The common approach to the synthesis of a new material involves reactions held at high temperatures under certain conditions such as heating in a robust vessel in the dark for a period until it is judged to have concluded. Analysis of the vessel contents afterward provides knowledge of the final products only. Intermediates that may form during the reaction process remain unknown. This lack of awareness of transient intermediates represents lost opportunities for discovering materials or understanding how the final products form. Here we present new results using an emerging in situ monitoring approach that shows high potential in discovering new compounds. In situ synchrotron X-ray diffraction studies were conducted in the Cs/Sn/P/Se system. Powder mixtures of Cs2Se2, Sn, and PSe2 were heated to 650 °C and then cooled to room temperature while acquiring consecutive in situ synchrotron diffraction patterns from the beginning to the end of the reaction process. The diffraction data was translated into the relationship of phases present versus temperature. Seven known crystalline phases were observed to form on warming in the experiment: Sn, Cs2Se3, Cs4Se16, Cs2Se5, Cs2Sn2Se6, Cs4P2Se9, and Cs2P2Se8. Six unknown phases were also detected; using the in situ synchrotron data as a guide three of them were isolated and characterized ex situ. These are Cs4Sn(P2Se6)2, α-Cs2SnP2Se6, and Cs4(Sn3Se8)[Sn(P2Se6)]2. Cs4(Sn3Se8)[Sn(P2Se6)]2 is a two-dimensional compound that behaves as an n-type doped semiconductor below 50 K and acts more like a semimetal at higher temperatures. Because all crystalline phases are revealed during the reaction, we call this approach "panoramic synthesis".
ASJC Scopus subject areas
- Colloid and Surface Chemistry