(CH3NH3)AuX4·H2O(X=Cl, Br) and (CH3NH3)AuCl4: Low-Band Gap Lead-Free Layered Gold Halide Perovskite Materials

doi:10.1002/chem.201901112

This content will become publicly available on May 14, 2020

Title: (CH ₃NH ₃)AuX ₄·H ₂O(X=Cl, Br) and (CH ₃NH ₃)AuCl ₄: Low-Band Gap Lead-Free Layered Gold Halide Perovskite Materials

Abstract

Perovskite solar cells have recently enabled power conversion efficiency comparable to established technologies such as silicon and cadmium telluride. Ongoing efforts to improve the stability of halide perovskites in ambient air has yielded promising results. However, the presence of toxic heavy element lead (Pb) remains a major concern requiring further attention. Herein, we report three new Pb-free hybrid organic–inorganic perovskite-type halides based on gold (Au), (CH ₃NH ₃)AuBr ₄·H ₂O ( 1), (CH ₃NH ₃)AuCl ₄·H ₂O ( 2), and (CH ₃NH ₃)AuCl ₄ ( 3). Hydrated compounds 1 and 2 crystallize in a brand-new structure type featuring perovskite-derived 2D layers and 1D chains based on pseudo-octahedral AuX ₆ building blocks. In contrast, the novel crystal structure of the solvent-free compound 3 shows an exotic non-perovskite quasi-2D layered structure containing edge- and corner-shared AuCl ₆ octahedra. The use of Au metal instead of Pb results in unprecedented low band gaps below 2.5 eV for single-layered metal chlorides and bromides. Moreover, at room temperature the three compounds show a weak blue emission due to the electronic transition between Au-6s and Au-5d, in agreement with the density function theory (DFT) calculation results. These findings are discussed in the context of viability ofmore »« less

Authors:

Worley, Chris ^[1];

^[1]; Roccanova, Rachel ^[1];

^[2];

^[1]

Univ. of Oklahoma, Norman, OK (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Publication Date:: 2019-05-14

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI Identifier:: 1545209

Alternate Identifier(s):: OSTI ID: 1530632

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Chemistry - A European Journal

Additional Journal Information:: Journal Volume: 25; Journal Issue: 42; Journal ID: ISSN 0947-6539

Publisher:: ChemPubSoc Europe

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 13 HYDRO ENERGY; 30 DIRECT ENERGY CONVERSION

Citation Formats


                    Worley, Chris, Yangui, Aymen, Roccanova, Rachel, Du, Mao‐Hua, and Saparov, Bayrammurad. (CH3NH3)AuX4·H2O(X=Cl, Br) and (CH3NH3)AuCl4: Low-Band Gap Lead-Free Layered Gold Halide Perovskite Materials.  United States: N. p., 2019. 
        Web.  doi:10.1002/chem.201901112.

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                    Worley, Chris, Yangui, Aymen, Roccanova, Rachel, Du, Mao‐Hua, & Saparov, Bayrammurad. (CH3NH3)AuX4·H2O(X=Cl, Br) and (CH3NH3)AuCl4: Low-Band Gap Lead-Free Layered Gold Halide Perovskite Materials.  United States.  doi:10.1002/chem.201901112.

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                    Worley, Chris, Yangui, Aymen, Roccanova, Rachel, Du, Mao‐Hua, and Saparov, Bayrammurad. Tue .  
        "(CH3NH3)AuX4·H2O(X=Cl, Br) and (CH3NH3)AuCl4: Low-Band Gap Lead-Free Layered Gold Halide Perovskite Materials".  United States.  doi:10.1002/chem.201901112.

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@article{osti_1545209,

  title        = {(CH3NH3)AuX4·H2O(X=Cl, Br) and (CH3NH3)AuCl4: Low-Band Gap Lead-Free Layered Gold Halide Perovskite Materials},

  author       = {Worley, Chris and Yangui, Aymen and Roccanova, Rachel and Du, Mao‐Hua and Saparov, Bayrammurad},

  abstractNote = {Perovskite solar cells have recently enabled power conversion efficiency comparable to established technologies such as silicon and cadmium telluride. Ongoing efforts to improve the stability of halide perovskites in ambient air has yielded promising results. However, the presence of toxic heavy element lead (Pb) remains a major concern requiring further attention. Herein, we report three new Pb-free hybrid organic–inorganic perovskite-type halides based on gold (Au), (CH3NH3)AuBr4·H2O (1), (CH3NH3)AuCl4·H2O (2), and (CH3NH3)AuCl4 (3). Hydrated compounds 1 and 2 crystallize in a brand-new structure type featuring perovskite-derived 2D layers and 1D chains based on pseudo-octahedral AuX6 building blocks. In contrast, the novel crystal structure of the solvent-free compound 3 shows an exotic non-perovskite quasi-2D layered structure containing edge- and corner-shared AuCl6 octahedra. The use of Au metal instead of Pb results in unprecedented low band gaps below 2.5 eV for single-layered metal chlorides and bromides. Moreover, at room temperature the three compounds show a weak blue emission due to the electronic transition between Au-6s and Au-5d, in agreement with the density function theory (DFT) calculation results. These findings are discussed in the context of viability of Au-based halides as alternatives for Pb-based halides for optoelectronic applications.},

  doi          = {10.1002/chem.201901112},

  journal      = {Chemistry - A European Journal},

  number       = 42,

  volume       = 25,

  place        = {United States},

  year         = {2019},

  month        = {5}

}

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Works referenced in this record:

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Similar Records

This content will become publicly available on May 14, 2020

Title: (CH 3NH 3)AuX 4·H 2O(X=Cl, Br) and (CH 3NH 3)AuCl 4: Low-Band Gap Lead-Free Layered Gold Halide Perovskite Materials

Abstract

Citation Formats

Generalized Gradient Approximation Made Simple journal, October 1996

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

SHELXT – Integrated space-group and crystal-structure determination journal, January 2015

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal, July 1996

Structural Phase Transitions of the Polymorphs of CsSnI3 by Means of Rietveld Analysis of the X-Ray Diffraction journal, May 1991

Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells journal, July 2014

Organic-Inorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors journal, October 1999

Air-Stable Molecular Semiconducting Iodosalts for Solar Cell Applications: Cs2SnI6 as a Hole Conductor journal, October 2014

Title: (CH ₃NH ₃)AuX ₄·H ₂O(X=Cl, Br) and (CH ₃NH ₃)AuCl ₄: Low-Band Gap Lead-Free Layered Gold Halide Perovskite Materials

Generalized Gradient Approximation Made Simple
journal, October 1996

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Structural Phase Transitions of the Polymorphs of CsSnI₃ by Means of Rietveld Analysis of the X-Ray Diffraction
journal, May 1991

Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells
journal, July 2014

Organic-Inorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors
journal, October 1999

Air-Stable Molecular Semiconducting Iodosalts for Solar Cell Applications: Cs₂SnI₆ as a Hole Conductor
journal, October 2014