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Zinc(II) and Cadmium(II) Complexes, [M(iPr2P(X)NC(Y)NC5H10-κ2-X,Y)2] (X and Y= O, S), as Single Source Precursors for Metal Sulfide Thin films

Abstract

Zinc(II) and cadmium(II) complexes of general formula [M(iPr2P(X)NC(Y)NC5H10-κ2-X,Y)2] (M = Zn, X=Y=S (4), X=S,Y=O (5), X=O, Y=S (6), and M= Cd, X=Y=S (7), X=S,Y=O (8), X=O, Y=S (9)), have been synthesized and characterized by elemental analysis, IR and NMR spectroscopy, and thermogravimetric analysis (TGA). SCXRD molecular structures of complexes 6, 7, and 9 revealed ligands binding the metal center in a bidentate fashion in an overall distorted tetrahedral coordination geometry. TGA showed 4-9 to decompose in a single step to their corresponding metal sulfides. Aerosol assisted chemical vapor deposition (AACVD) at 450℃ and subsequent annealing at 600 ℃ was used to examine 4-9 as single source precursors (SSPs) for the deposition of nanostructured metal sulfide thin films (4F-6F unannealed ZnS films and 7F-9F unannealed CdS films). GIXRD confirmed that resultant films have nanocrystalline hexagonal structure with (002) preferential orientation, except for 9F, and grain size varied from 15 to 24 nm. Scanning electron and atomic force microscopy (SEM and AFM) images revealed relatively dense grain columnar structure. The elemental composition and mapping studies showed near-stoichiometric MS thin films homogeneously distributed. As-deposited ZnS thin films 4F-6F) displayed phosphorus content between 6.4 and 8.2, while CdS films showed no phosphorus content except for 9F, which showed P 2%. Films optical properties as direct optical energy gap (Eg), Raman and photoluminescence (PL) displayed some differences related to the employed SSP, being more significant for films obtained from precursor containing hybrid ligand -P(O)NC(S)- (3), which showed the major phosphorus content (6F and 9F). Sharp excitonic emission at room temperature, as well as multiple Raman overtones, shows the high optical quality of the investigated CdS thin films. The PL spectra of ZnS films showed emissions attributed to the near band edge and different crystalline imperfections such as vacancies and interstitials

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Supplementary files

Article information


Submitted
25 Mar 2020
Accepted
16 May 2020
First published
22 May 2020

New J. Chem., 2020, Accepted Manuscript
Article type
Paper

Zinc(II) and Cadmium(II) Complexes, [M(iPr2P(X)NC(Y)NC5H10-κ2-X,Y)2] (X and Y= O, S), as Single Source Precursors for Metal Sulfide Thin films

V. Flores-Romero, O. L. García-Guzmán, A. Aguirre-Bautista, I. D. Rojas-Montoya, V. Garcia-Montalvo, M. Rivera, O. Jiménez-Sandoval, M. A. Muñoz-Hernández and S. Hernandez-Ortega, New J. Chem., 2020, Accepted Manuscript , DOI: 10.1039/D0NJ01465F

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