Aerosol-Assisted Chemical Vapor Deposition of ZnS from Thioureide Single Source Precursors

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Abstract

A family of 12 zinc(II) thoureide complexes, of the general form [{L}ZnMe], [{L}Zn{N(SiMe 3 ) 2 }], and [{L} 2 Zn], have been synthesized by direct reaction of the thiourea pro-ligands i PrN(H)CS(NMe 2 ) H[L 1 ], CyN(H)CS(NMe 2 ) H[L 3 ], t BuN(H)CS(NMe 2 ) H[L 2 ], and MesN(H)CS(NMe 2 ) H[L 4 ] with either ZnMe 2 (1:1) or Zn{N(SiMe 3 ) 2 } 2 (1:1 and 2:1) and characterized by elemental analysis, NMR spectroscopy, and thermogravimetric analysis (TGA). The molecular structures of complexes [{L 1 }ZnMe] 2 (1), [{L 2 }ZnMe] 2 ] (2), [{L 3 }ZnMe] âž (3), [{L 4 }ZnMe] 2 ] (4), [{L 1 }Zn{N(SiMe 3 ) 2 }] 2 (5), [{L 2 }Zn{N(SiMe 3 ) 2 }] 2 (6), [{L 3 }Zn{N(SiMe 3 ) 2 }] 2 ] (7), [{L 4 }Zn{N(SiMe 3 ) 2 }] 2 ] (8), [{L 1 } 2 Zn] 2 (9), and [{L 4 } 2 Zn] 2 (12) have been unambiguously determined using single crystal X-ray diffraction studies. Thermogravimetric analysis has been used to assess the viability of complexes 1-12 as single source precursors for the formation of ZnS. On the basis of TGA data compound 9 was investigated for its utility as a single source precursor to deposit ZnS films on silica-coated glass and crystalline silicon substrates at 150, 200, 250, and 300 °C using an aerosol assisted chemical vapor deposition (AACVD) method. The resultant films were confirmed to be hexagonal-ZnS by Raman spectroscopy and PXRD, and the surface morphologies were examined by SEM and AFM analysis. Thin films deposited from (9) at 250 and 300 °C were found to be comprised of more densely packed and more highly crystalline ZnS than films deposited at lower temperatures. The electronic properties of the ZnS thin films were deduced by UV-Vis spectroscopy to be very similar and displayed absorption behavior and band gap (E g = 3.711-3.772 eV) values between those expected for bulk cubic-ZnS (E g = 3.54 eV) and hexagonal-ZnS (E g = 3.91 eV).

Original languageEnglish
Pages (from-to)2784-2797
Number of pages14
JournalInorganic Chemistry
Volume58
Issue number4
Early online date4 Feb 2019
DOIs
Publication statusPublished - 18 Feb 2019

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{7baa9ccb7b324b92b7a224af6f2ff896,
title = "Aerosol-Assisted Chemical Vapor Deposition of ZnS from Thioureide Single Source Precursors",
abstract = "A family of 12 zinc(II) thoureide complexes, of the general form [{L}ZnMe], [{L}Zn{N(SiMe 3 ) 2 }], and [{L} 2 Zn], have been synthesized by direct reaction of the thiourea pro-ligands i PrN(H)CS(NMe 2 ) H[L 1 ], CyN(H)CS(NMe 2 ) H[L 3 ], t BuN(H)CS(NMe 2 ) H[L 2 ], and MesN(H)CS(NMe 2 ) H[L 4 ] with either ZnMe 2 (1:1) or Zn{N(SiMe 3 ) 2 } 2 (1:1 and 2:1) and characterized by elemental analysis, NMR spectroscopy, and thermogravimetric analysis (TGA). The molecular structures of complexes [{L 1 }ZnMe] 2 (1), [{L 2 }ZnMe] 2 ] (2), [{L 3 }ZnMe] {\^a}ž (3), [{L 4 }ZnMe] 2 ] (4), [{L 1 }Zn{N(SiMe 3 ) 2 }] 2 (5), [{L 2 }Zn{N(SiMe 3 ) 2 }] 2 (6), [{L 3 }Zn{N(SiMe 3 ) 2 }] 2 ] (7), [{L 4 }Zn{N(SiMe 3 ) 2 }] 2 ] (8), [{L 1 } 2 Zn] 2 (9), and [{L 4 } 2 Zn] 2 (12) have been unambiguously determined using single crystal X-ray diffraction studies. Thermogravimetric analysis has been used to assess the viability of complexes 1-12 as single source precursors for the formation of ZnS. On the basis of TGA data compound 9 was investigated for its utility as a single source precursor to deposit ZnS films on silica-coated glass and crystalline silicon substrates at 150, 200, 250, and 300 °C using an aerosol assisted chemical vapor deposition (AACVD) method. The resultant films were confirmed to be hexagonal-ZnS by Raman spectroscopy and PXRD, and the surface morphologies were examined by SEM and AFM analysis. Thin films deposited from (9) at 250 and 300 °C were found to be comprised of more densely packed and more highly crystalline ZnS than films deposited at lower temperatures. The electronic properties of the ZnS thin films were deduced by UV-Vis spectroscopy to be very similar and displayed absorption behavior and band gap (E g = 3.711-3.772 eV) values between those expected for bulk cubic-ZnS (E g = 3.54 eV) and hexagonal-ZnS (E g = 3.91 eV).",
author = "Hannah Sullivan and James Parish and Prem Thongchai and Gabriele Kociok-Kohn and Michael Hill and Andrew Johnson",
year = "2019",
month = "2",
day = "18",
doi = "10.1021/acs.inorgchem.8b03363",
language = "English",
volume = "58",
pages = "2784--2797",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Aerosol-Assisted Chemical Vapor Deposition of ZnS from Thioureide Single Source Precursors

AU - Sullivan, Hannah

AU - Parish, James

AU - Thongchai, Prem

AU - Kociok-Kohn, Gabriele

AU - Hill, Michael

AU - Johnson, Andrew

PY - 2019/2/18

Y1 - 2019/2/18

N2 - A family of 12 zinc(II) thoureide complexes, of the general form [{L}ZnMe], [{L}Zn{N(SiMe 3 ) 2 }], and [{L} 2 Zn], have been synthesized by direct reaction of the thiourea pro-ligands i PrN(H)CS(NMe 2 ) H[L 1 ], CyN(H)CS(NMe 2 ) H[L 3 ], t BuN(H)CS(NMe 2 ) H[L 2 ], and MesN(H)CS(NMe 2 ) H[L 4 ] with either ZnMe 2 (1:1) or Zn{N(SiMe 3 ) 2 } 2 (1:1 and 2:1) and characterized by elemental analysis, NMR spectroscopy, and thermogravimetric analysis (TGA). The molecular structures of complexes [{L 1 }ZnMe] 2 (1), [{L 2 }ZnMe] 2 ] (2), [{L 3 }ZnMe] âž (3), [{L 4 }ZnMe] 2 ] (4), [{L 1 }Zn{N(SiMe 3 ) 2 }] 2 (5), [{L 2 }Zn{N(SiMe 3 ) 2 }] 2 (6), [{L 3 }Zn{N(SiMe 3 ) 2 }] 2 ] (7), [{L 4 }Zn{N(SiMe 3 ) 2 }] 2 ] (8), [{L 1 } 2 Zn] 2 (9), and [{L 4 } 2 Zn] 2 (12) have been unambiguously determined using single crystal X-ray diffraction studies. Thermogravimetric analysis has been used to assess the viability of complexes 1-12 as single source precursors for the formation of ZnS. On the basis of TGA data compound 9 was investigated for its utility as a single source precursor to deposit ZnS films on silica-coated glass and crystalline silicon substrates at 150, 200, 250, and 300 °C using an aerosol assisted chemical vapor deposition (AACVD) method. The resultant films were confirmed to be hexagonal-ZnS by Raman spectroscopy and PXRD, and the surface morphologies were examined by SEM and AFM analysis. Thin films deposited from (9) at 250 and 300 °C were found to be comprised of more densely packed and more highly crystalline ZnS than films deposited at lower temperatures. The electronic properties of the ZnS thin films were deduced by UV-Vis spectroscopy to be very similar and displayed absorption behavior and band gap (E g = 3.711-3.772 eV) values between those expected for bulk cubic-ZnS (E g = 3.54 eV) and hexagonal-ZnS (E g = 3.91 eV).

AB - A family of 12 zinc(II) thoureide complexes, of the general form [{L}ZnMe], [{L}Zn{N(SiMe 3 ) 2 }], and [{L} 2 Zn], have been synthesized by direct reaction of the thiourea pro-ligands i PrN(H)CS(NMe 2 ) H[L 1 ], CyN(H)CS(NMe 2 ) H[L 3 ], t BuN(H)CS(NMe 2 ) H[L 2 ], and MesN(H)CS(NMe 2 ) H[L 4 ] with either ZnMe 2 (1:1) or Zn{N(SiMe 3 ) 2 } 2 (1:1 and 2:1) and characterized by elemental analysis, NMR spectroscopy, and thermogravimetric analysis (TGA). The molecular structures of complexes [{L 1 }ZnMe] 2 (1), [{L 2 }ZnMe] 2 ] (2), [{L 3 }ZnMe] âž (3), [{L 4 }ZnMe] 2 ] (4), [{L 1 }Zn{N(SiMe 3 ) 2 }] 2 (5), [{L 2 }Zn{N(SiMe 3 ) 2 }] 2 (6), [{L 3 }Zn{N(SiMe 3 ) 2 }] 2 ] (7), [{L 4 }Zn{N(SiMe 3 ) 2 }] 2 ] (8), [{L 1 } 2 Zn] 2 (9), and [{L 4 } 2 Zn] 2 (12) have been unambiguously determined using single crystal X-ray diffraction studies. Thermogravimetric analysis has been used to assess the viability of complexes 1-12 as single source precursors for the formation of ZnS. On the basis of TGA data compound 9 was investigated for its utility as a single source precursor to deposit ZnS films on silica-coated glass and crystalline silicon substrates at 150, 200, 250, and 300 °C using an aerosol assisted chemical vapor deposition (AACVD) method. The resultant films were confirmed to be hexagonal-ZnS by Raman spectroscopy and PXRD, and the surface morphologies were examined by SEM and AFM analysis. Thin films deposited from (9) at 250 and 300 °C were found to be comprised of more densely packed and more highly crystalline ZnS than films deposited at lower temperatures. The electronic properties of the ZnS thin films were deduced by UV-Vis spectroscopy to be very similar and displayed absorption behavior and band gap (E g = 3.711-3.772 eV) values between those expected for bulk cubic-ZnS (E g = 3.54 eV) and hexagonal-ZnS (E g = 3.91 eV).

UR - http://www.scopus.com/inward/record.url?scp=85061229555&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.8b03363

DO - 10.1021/acs.inorgchem.8b03363

M3 - Article

VL - 58

SP - 2784

EP - 2797

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 4

ER -