Synthesis of BaZrS₃ and BaHfS₃ Chalcogenide Perovskite Films Using Single‐Phase Molecular Precursors at Moderate Temperatures

Abstract

Chalcogenide perovskites have garnered interest for applications in semiconductor devices due to their excellent predicted optoelectronic properties and stability. However, high synthesis temperatures have historically made these materials incompatible with the creation of photovoltaic devices. Here, we demonstrate the solution processed synthesis of luminescent BaZrS3 and BaHfS3 chalcogenide perovskite films using single‐phase molecular precursors at sulfurization temperatures of 575 °C and sulfurization times as short as one hour. These molecular precursor inks were synthesized using known carbon disulfide insertion chemistry to create Group 4 metal dithiocarbamates, and this chemistry was extended to create species, such as barium dithiocarboxylates, that have never been reported before. These findings, with added future research, have the potential to yield fully solution processed thin films of chalcogenide perovskites for various optoelectronic applications.

Solution-phase synthesis of group 3–5 transition metal chalcogenide inorganic nanomaterials

“…40 This issue was circumvented in a more recent report by Agrawal in collaboration with the Bart group, in this case using true solution-phase molecular precursors for thin film fabrication. 46 In this report, a barium bis(dithiocarboxylate) complex and a zirconium tetrakis(dithiocarbamate) complex, both of which are generated in situ by insertion reactions of CS 2 into the appropriate precursor complex, are combined in pyridine solution, deposited by blade-coating, annealed, and sulfurized at 575 1C to produce BaZrS 3 (Fig. 8…”

“…However, Agrawal and Bart have reported the preparation of BaHfS 3 thin films from solution-phase molecular precursors, by an extension of the protocols described above for the preparation of BaZrS 3 thin films. 46…”

“…Given all these considerations, the scope of precursors for the group 4 transition metals remains fairly limited, especially for the formation of ternary species where the reactivity, solubility, and mutual interactions of multiple metal precursors must be considered. New precursors such as metal thiolates and metal dithiocarboxylates (some of which have already been applied in thin-film preparation by Bart and Agrawal) 40,46 or metal sulfide clusters could be considered. Sulfur-and selenium-containing complexes which have previously been used for chemical vapor deposition (CVD) of thin films provide another collection of possible single-source-precursor complexes.…”

Ti Alloying as a Route to BaZrS3 Chalcogenide Perovskite with Enhanced Photovoltaic Performance

“…To tackle the toxicity and stability issues of inorganic–organic lead-halide-based perovskites, chalcogenide perovskites have been viewed as an alternative material of semiconductors for optoelectronic and solar cell applications . Numerous investigations have reported various chalcogenide perovskites for excellent efficiency photovoltaic cells and photoelectrocatalytic water splitting. − Among these inorganic chalcogenides based on perovskites, BaZrS 3 is a good contender for a solar cell absorber because it has an extraordinarily high near-edge absorption coefficient of more than 10 5 cm –1 . ,, Dependent upon manufacturing circumstances, this material also has a respectable room-temperature mobility, varying from 2.3 to 13.7 cm 2 V –1 s –1 . BaZrS 3 exhibits band gap values experimentally ranging between 1.74 and 1.94 eV. − BaZrS 3 also exhibits higher structural stability and moisture stability .…”

“…Numerous investigations have reported various chalcogenide perovskites for excellent efficiency photovoltaic cells and photoelectrocatalytic water splitting. − Among these inorganic chalcogenides based on perovskites, BaZrS 3 is a good contender for a solar cell absorber because it has an extraordinarily high near-edge absorption coefficient of more than 10 5 cm –1 . ,, Dependent upon manufacturing circumstances, this material also has a respectable room-temperature mobility, varying from 2.3 to 13.7 cm 2 V –1 s –1 . BaZrS 3 exhibits band gap values experimentally ranging between 1.74 and 1.94 eV. − BaZrS 3 also exhibits higher structural stability and moisture stability . It also showed that the optical absorption coefficient of BaZrS 3 is highly remarkable compared to all of the other useful solar cell absorbers, such as GaAs, CuInSe 2 , and MAPbI 3 .…”