DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Journal Article · · Chemistry - A European Journal

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.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1545209
Alternate ID(s):
OSTI ID: 1530632
Journal Information:
Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 42 Vol. 25; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English

References (107)

Synthesis, characterization and phase transitions of the inorganic–organic layered perovskite-type hybrids [(C n H 2n+1 NH 3 ) 2 PbI 4 ], n = 7, 8, 9 and 10 journal January 2012
Bismuth Based Hybrid Perovskites A 3 Bi 2 I 9 (A: Methylammonium or Cesium) for Solar Cell Application journal September 2015
Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells journal July 2014
All-inorganic perovskite nanocrystal scintillators journal August 2018
Thin-Film Preparation and Characterization of Cs 3 Sb 2 I 9 : A Lead-Free Layered Perovskite Semiconductor journal August 2015
Cs 2 InAgCl 6 : A New Lead-Free Halide Double Perovskite with Direct Band Gap journal January 2017
New Contributions to the Optics of Intensely Light-Scattering Materials Part I journal January 1948
Perovskite Solar Cells: Beyond Methylammonium Lead Iodide journal February 2015
Molecular engineering of perovskite photodetectors: recent advances in materials and devices journal January 2018
Quantifying the Potential for Lead Pollution from Halide Perovskite Photovoltaics journal August 2015
Recycling Perovskite Solar Cells To Avoid Lead Waste journal May 2016
Attaining High Photovoltaic Efficiency and Stability with Multidimensional Perovskites journal November 2018
Structural Diversity in White-Light-Emitting Hybrid Lead Bromide Perovskites journal September 2018
Structural characterization, vibrational, optical properties and DFT investigation of a new luminescent organic–inorganic material: (C6H14N)3Bi2I9 journal May 2015
Broadband Emission in Hybrid Organic–Inorganic Halides of Group 12 Metals journal December 2018
Broadband Emission in a New Two-Dimensional Cd-Based Hybrid Perovskite journal January 2018
Under the spotlight: The organic–inorganic hybrid halide perovskite for optoelectronic applications journal June 2015
Control of the white-light emission in the mixed two-dimensional hybrid perovskites (C 6 H 11 NH 3 ) 2 [PbBr 4−x I x ] journal March 2017
Hybrid Perovskites for Photovoltaics: Charge-Carrier Recombination, Diffusion, and Radiative Efficiencies journal December 2015
A critical review on tin halide perovskite solar cells journal January 2017
Strained hybrid perovskite thin films and their impact on the intrinsic stability of perovskite solar cells journal November 2017
Chemistry and structure in Acta Crystallographica Section C text January 2015
Recent progress in organometal halide perovskite photodetectors journal January 2018
Recombination in Perovskite Solar Cells: Significance of Grain Boundaries, Interface Traps, and Defect Ions journal April 2017
Chemistry and structure in Acta Crystallographica Section C journal January 2015
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Bandgap Narrowing in Bi-Doped CH 3 NH 3 PbCl 3 Perovskite Single Crystals and Thin Films journal August 2017
SHELXT – Integrated space-group and crystal-structure determination journal January 2015
Single-crystalline layered metal-halide perovskite nanowires for ultrasensitive photodetectors journal July 2018
High spectral resolution of gamma-rays at room temperature by perovskite CsPbBr3 single crystals journal April 2018
Degradation in perovskite solar cells stored under different environmental conditions journal July 2017
Electronegativity values from thermochemical data journal June 1961
Bis(pentane-1,5-diammonium) decaiodotriplumbate(II) journal April 2004
Perovskite Solar Cells and Devices at EPFL Valais Wallis journal September 2016
Structural diversity and retro-crystal engineering analysis of iodometalate hybrids journal January 2009
Synthesis, Crystal and Electronic Structures, and Optical Properties of (CH 3 NH 3 ) 2 CdX 4 (X = Cl, Br, I) journal November 2017
Highly Stable, New, Organic-Inorganic Perovskite (CH 3 NH 3 ) 2 PdBr 4 : Synthesis, Structure, and Physical Properties journal March 2018
Nanocrystalline Perovskite Hybrid Photodetectors with High Performance in Almost Every Figure of Merit journal December 2017
Optical Investigation of Broadband White-Light Emission in Self-Assembled Organic–Inorganic Perovskite (C 6 H 11 NH 3 ) 2 PbBr 4 journal October 2015
Progress on lead-free metal halide perovskites for photovoltaic applications: a review journal March 2017
The one-dimensional organic–inorganic hybrid: catena -poly[bis[1-(3-ammoniopropyl)-1 H -imidazolium] [[iodidoplumbate(II)]-tri-μ-iodido-plumbate(II)-tri-μ-iodido-[iodidoplumbate(II)]-di-μ-iodido]] journal March 2011
High-efficiency perovskite–polymer bulk heterostructure light-emitting diodes journal November 2018
Ultralarge All-Inorganic Perovskite Bulk Single Crystal for High-Performance Visible-Infrared Dual-Modal Photodetectors journal May 2017
Structural Phase Transitions of the Polymorphs of CsSnI3 by Means of Rietveld Analysis of the X-Ray Diffraction journal May 1991
Strained hybrid perovskite thin films and their impact on the intrinsic stability of perovskite solar cells text January 2017
Fabrication of Lead-Free (CH 3 NH 3 ) 3 Bi 2 I 9 Perovskite Photovoltaics in Ethanol Solvent journal September 2017
The resistivity of mixed valence compound Cs2Au2Cl6 at high pressure and low temperatures journal October 1974
Solar cell efficiency tables (version 52)
  • Green, Martin A.; Hishikawa, Yoshihiro; Dunlop, Ewan D.
  • Progress in Photovoltaics: Research and Applications, Vol. 26, Issue 7 https://doi.org/10.1002/pip.3040
journal June 2018
Low-temperature solution-processed wavelength-tunable perovskites for lasing journal March 2014
High-resolution X-ray luminescence extension imaging journal February 2021
Solution-processed hybrid perovskite photodetectors with high detectivity journal November 2014
Rb 4 Ag 2 BiBr 9 : A Lead-Free Visible Light Absorbing Halide Semiconductor with Improved Stability journal February 2019
Perovskite Solar Cells Go Lead Free journal December 2017
Properties of CH 3 NH 3 PbX 3 (X = I, Br, Cl) Powders as Precursors for Organic/Inorganic Solar Cells journal November 2014
Two‐Step Structure Phase Transition, Dielectric Anomalies, and Thermochromic Luminescence Behavior in a Direct Band Gap 2D Corrugated Layer Lead Chloride Hybrid of [(CH 3 ) 4 N ] 4 Pb 3 Cl 10 journal March 2019
Synthesis and Properties of a Lead-Free Hybrid Double Perovskite: (CH 3 NH 3 ) 2 AgBiBr 6 journal January 2017
Computational Design of Two-Dimensional Perovskites with Functional Organic Cations journal March 2018
Band Gaps of the Lead-Free Halide Double Perovskites Cs 2 BiAgCl 6 and Cs 2 BiAgBr 6 from Theory and Experiment journal June 2016
(C 6 H 5 C 2 H 4 NH 3 ) 2 GeI 4 : A Layered Two-Dimensional Perovskite with Potential for Photovoltaic Applications journal September 2017
Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design journal March 2016
Bulk crystal growth of hybrid perovskite material CH 3 NH 3 PbI 3 journal January 2015
Electronic structure of the gold complexes Cs 2 Au 2 X 6   ( X =I, Br, and Cl) journal March 1999
High-efficiency perovskite-polymer bulk heterostructure light-emitting diodes text January 2018
Synthesis and crystal structures of iodoplumbate chains, ribbons and rods with new structural types journal January 2001
Mixed Dimensional 2D/3D Hybrid Perovskite Absorbers: The Future of Perovskite Solar Cells? journal December 2018
Cs2AgBiBr6 single-crystal X-ray detectors with a low detection limit journal October 2017
(CH 3 NH 3 ) 2 PdCl 4 : A Compound with Two-Dimensional Organic-Inorganic Layered Perovskite Structure journal January 2016
Attaining High Photovoltaic Efficiency and Stability with Multidimensional Perovskites. text January 2018
Lead-free germanium iodide perovskite materials for photovoltaic applications journal January 2015
Fabrication of self-assembled palladium nanosheets using layered organic/inorganic hybrid as the template journal December 2005
Color-stable highly luminescent sky-blue perovskite light-emitting diodes journal August 2018
Near-Unity Photoluminescence Quantum Yield in Blue-Emitting Cs 3 Cu 2 Br 5– x I x (0 ≤ x ≤ 5) journal February 2019
Structural phase transition causing anomalous photoluminescence behavior in perovskite (C 6 H 11 NH 3 ) 2 [PbI 4 ] journal December 2015
Dimensionality engineering of hybrid halide perovskite light absorbers journal November 2018
Two-Dimensional Hybrid Halide Perovskites: Principles and Promises journal November 2018
Graphdiyne as a Host Active Material for Perovskite Solar Cell Application journal October 2018
Efficient room temperature aqueous Sb 2 S 3 synthesis for inorganic–organic sensitized solar cells with 5.1% efficiencies journal January 2015
Lead-free solid-state organic–inorganic halide perovskite solar cells journal May 2014
How transport layer properties affect perovskite solar cell performance: insights from a coupled charge transport/ion migration model journal January 2019
High-performance direct conversion X-ray detectors based on sintered hybrid lead triiodide perovskite wafers journal June 2017
Organic-inorganic electronics journal January 2001
High Chloride Doping Levels Stabilize the Perovskite Phase of Cesium Lead Iodide journal May 2016
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Perovskite-based low-cost and high-efficiency hybrid halide solar cells journal January 2014
Generalized Gradient Approximation Made Simple journal October 1996
Air-Stable Molecular Semiconducting Iodosalts for Solar Cell Applications: Cs2SnI6 as a Hole Conductor
  • Lee, Byunghong; Stoumpos, Constantinos C.; Zhou, Nanjia
  • Journal of the American Chemical Society, Vol. 136, Issue 43, p. 15379-15385 https://doi.org/10.1021/ja508464w
journal October 2014
Organic-Inorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors journal October 1999
Perovskite photonic sources journal April 2016
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal May 2021
Optical Properties and Electronic Structure of Amorphous Germanium journal January 1966
Mixed Valence Perovskite Cs 2 Au 2 I 6 : A Potential Material for Thin-Film Pb-Free Photovoltaic Cells with Ultrahigh Efficiency journal February 2018
Laser cooling of organic–inorganic lead halide perovskites journal December 2015
High Detectivity and Rapid Response in Perovskite CsPbBr 3 Single-Crystal Photodetector journal February 2017
Broadband Emission with a Massive Stokes Shift from Sulfonium Pb–Br Hybrids journal August 2017
Toward Lead-Free Perovskite Solar Cells journal November 2016
Perovskite Solar Cells Go Lead Free journal December 2017
Evidence and detailed study of a second-order phase transition in the (C 6 H 11 NH 3 ) 2 [PbI 4 ] organic-inorganic hybrid material journal March 2015
High-efficiency perovskite–polymer bulk heterostructure light-emitting diodes text January 2018
Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells journal June 2017
Thin Films and Solar Cells Based on Semiconducting Two-Dimensional Ruddlesden–Popper (CH 3 (CH 2 ) 3 NH 3 ) 2 (CH 3 NH 3 ) n −1 Sn n I 3 n +1 Perovskites journal April 2017
Synthesis, crystal structure, absorption properties, photoelectric behavior of organic-inorganic hybrid (CH 3 NH 3 ) 2 CoCl 4 : Photoelectric Behavior of (CH3NH3)2CoCl4 journal February 2019
Stability of Metal Halide Perovskite Solar Cells journal September 2015
Hybrid Organic–Inorganic Halides (C 5 H 7 N 2 ) 2 MBr 4 (M = Hg, Zn) with High Color Rendering Index and High-Efficiency White-Light Emission journal March 2019
Toxicity of organometal halide perovskite solar cells journal February 2016
Rapid and robust spatiotemporal dynamics of the first-order phase transition in crystals of the organic-inorganic perovskite (C12H25NH3)2PbI4 journal November 2015
Yellowish White-Light Emission Involving Resonant Energy Transfer in a New One-Dimensional Hybrid Material: (C 9 H 10 N 2 )PbCl 4 journal September 2018
Beyond methylammonium lead iodide: prospects for the emergent field of ns 2 containing solar absorbers journal January 2017

Cited By (3)

Lead-Free Perovskites for Lighting and Lasing Applications: A Minireview journal November 2019
Lead-Free Perovskites for Lighting and Lasing Applications: A Minireview journal November 2019
Additive-assisted synthesis and optoelectronic properties of (CH 3 NH 3 ) 4 Bi 6 I 22 journal January 2020