Atamtürk, Ufuk ORCID: 0000-0002-5627-5375 (2023). Chemical Vapor Deposition of Molecular Thiolates of Bismuth, Tin and Lead & Multinuclear NMR Studies on Lead Halide Perovskites. PhD thesis, Universität zu Köln.

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The first part of this thesis (Chapters 3 to 5) describes the investigation on molecular single-source precursor and their successful application in the chemical vapor deposition (CVD) of Bi2S3, SnS and PbS. In the second part (Chapter 6) light was shed on the dynamics existent in the precursor solutions (c_solute ≥ 0.4 M) used for the fabrication of APbI3 (A+ = CH3NH3 +, Cs+) lead halide perovskites. Bismuth(III) alkylthiolates, Bi(SR)3 (R= –But (1a); –Pri (1b)) were applied in the CVD process as single-source precursors for both Bi2S3 and Bi. The CVD of Bi(SBut)3 (1a) produced highly oriented and uniformly shaped 2D Bi2S3 platelets. Elemental Bi was obtained from Bi(SPri)3 (1b) in unprecedented morphologies, as the first example of elemental bismuth by non-classical crystallization. Moreover, was the crystal structure of Bi(SBut)3 (1a) determined. The synthesis of the molecular precursor [Sn(SBut)(tfb-dmeda)] (2a) is reported introducing a ‘launch vehicle’-effect, thus remarkably increasing its volatility. (2a) was characterized by single crystal X-ray diffraction analysis, EI-MS, multinuclear (1H, 13C, 19F and 119Sn) and variable-temperature 1D and 2D NMR studies. The precursor (2a) was used to deposit SnS thin films by CVD on different substrates at different temperatures (300℃–450℃) and times (15 min–60 min). The crystal structure and chemical shifts δ207Pb of lead(II) alkylthiolates Pb(SBut)2 (3a) and Pb(SBui)2 (3c) is presented. The application of Pb(SPri)2 (3b) as single-source precursor for the CVD of PbS is reported. The EI-MS analysis of (3b) and (3c) revealed the molecules as monomeric in the gas phase and (3c) also as dinuclear species. The fundamental solution chemistry of PbI2 and PbI2+AI (A+ = Cs+, CH3NH3 +) in DMSO and DMF was elucidated, by means of multinuclear 207Pb-, 133Cs- and 1H-NMR titration and dilution experiments. By establishing the link between solution and solid-state 207Pb-NMR spectroscopy, which was also mirrored in the linewidths of the 133Cs- and 1H-NMR resonances, it could be shown that PbI2 and PbI2 + AI exist in dynamic equilibria in DMSO and DMF solution as polynuclear condensed PbI6-octahedra. Hereby the acceptor property of the solvents was identified as key feature that governs the solute-solvent interactions.

Item Type: Thesis (PhD thesis)
CreatorsEmailORCIDORCID Put Code
URN: urn:nbn:de:hbz:38-650875
Date: 28 February 2023
Place of Publication: Köln
Language: English
Faculty: Faculty of Mathematics and Natural Sciences
Divisions: Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects: Chemistry and allied sciences
Uncontrolled Keywords:
bismuth thiolates; CVD; Bi2S3; BismuthEnglish
tin(II) thiolates; lead thiolates;English
multinuclear NMR; 133Cs; 207Pb; perovskitesEnglish
Date of oral exam: 9 January 2023
NameAcademic Title
Mathur, SanjayProfessor
Axel, KleinProfessor
Refereed: Yes


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