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Highly Absorbing Lead-Free Semiconductor Cu₂AgBiI₆ for Photovoltaic Applications from the Quaternary CuI-AgI-BiI₃ Phase Space.

ABSTRACT: Since the emergence of lead halide perovskites for photovoltaic research, there has been mounting effort in the search for alternative compounds with improved or complementary physical, chemical, or optoelectronic properties. Here, we report the discovery of Cu₂AgBiI₆: a stable, inorganic, lead-free wide-band-gap semiconductor, well suited for use in lead-free tandem photovoltaics. We measure a very high absorption coefficient of 1.0 × 10⁵ cm^-1 near the absorption onset, several times that of CH₃NH₃PbI₃. Solution-processed Cu₂AgBiI₆ thin films show a direct band gap of 2.06(1) eV, an exciton binding energy of 25 meV, a substantial charge-carrier mobility (1.7 cm² V^-1 s^-1), a long photoluminescence lifetime (33 ns), and a relatively small Stokes shift between absorption and emission. Crucially, we solve the structure of the first quaternary compound in the phase space among CuI, AgI and BiI₃. The structure includes both tetrahedral and octahedral species which are open to compositional tuning and chemical substitution to further enhance properties. Since the proposed double-perovskite Cs₂AgBiI₆ thin films have not been synthesized to date, Cu₂AgBiI₆ is a valuable example of a stable Ag⁺/Bi³⁺ octahedral motif in a close-packed iodide sublattice that is accessed via the enhanced chemical diversity of the quaternary phase space.

SUBMITTER: Sansom HC

PROVIDER: S-EPMC8041282 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The reactions of N-heterocyclic carbene CuI and AgI halides with potassium thio- or seleno-cyanate gave unexpected products. The attempted substitution reaction of bromido-(1,3-dibenzyl-4,5-di-phenyl-imidazol-2-yl-idene)silver (NHC*-Ag-Br) with KSCN yielded bis-[bis-(1,3-dibenzyl-4,5-di-phenyl-imidazol-2-yl-idene)silver(I)] tris-(thio-cyanato)-argentate(I) diethyl ether disolvate, [Ag(C29H24N2)2][Ag(NCS)3]·2C4H10O or [NHC*2Ag]2[Ag(SCN)3]·2Et2O, (1), while reaction with KSeCN led to bis-(μ-1,3-dibenzyl-4,5-diphenyl-2-seleno-imidazole-κ2 Se:Se)bis-[bromido-(1,3-dibenzyl-4,5-diphenyl-2-seleno-imid-azole-κSe)silver(I)] di-chloro-methane hexa-solvate, [Ag2Br2(C29H24N2Se)4]·6CH2Cl2 or (NHC*Se)4Ag2Br2·6CH2Cl2, (2), via oxidation of the NHC* fragment to 2-seleno-imidazole. This oxidation was observed again in the reaction of NHC*-Cu-Br with KSeCN, yielding catena-poly[[[(1,3-dibenzyl-4,5-diphenyl-2-seleno-imidazole-κSe)copper(I)]-μ-cyanido-κ2 C:N] aceto-nitrile monosolvate], {[Cu(CN)(C29H24N2Se)]·C2H3N} n or NHC*Se-CuCN·CH3CN, (3). Compound (1) represents an organic/inorganic salt with AgI in a linear coordination in each of the two cations and in a trigonal coordination in the anion, accompanied by diethyl ether solvent mol-ecules. The tri-blade boomerang-shaped complex anion [Ag(SCN)3]2- present in (1) is characterized by X-ray diffraction for the first time. Compound (2) comprises an isolated centrosymmetric mol-ecule with AgI in a distorted tetra-hedral BrSe3 coordination, together with di-chloro-methane solvent mol-ecules. Compound (3) exhibits a linear polymeric 1 ∞[Cu-C≡N-Cu-] chain structure with a seleno-imidazole moiety additionally coordinating to each CuI atom, and completed by aceto-nitrile solvent mol-ecules. Electron densities associated with an additional ether solvent mol-ecule in (1) and two additional di-chloro-methane solvent mol-ecules in (2) were removed with the SQUEEZE procedure [Spek (2015 ▸). Acta Cryst. C71, 9-18] in PLATON.

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Highly Absorbing Lead-Free Semiconductor Cu₂AgBiI₆ for Photovoltaic Applications from the Quaternary CuI-AgI-BiI₃ Phase Space.

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Highly Absorbing Lead-Free Semiconductor Cu₂AgBiI₆ for Photovoltaic Applications from the Quaternary CuI-AgI-BiI₃ Phase Space.