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

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Abstract

A family of twelve Zinc(II) thoureide complexes, of the general form [{L}ZnMe], [{L}Zn{N(SiMe3)2}] and [{L}2Zn], have been synthesized by direct reaction of the thiourea pro-ligands iPrN(H)CS(NMe2) H[L1], CyN(H)CS(NMe2) H[L2], tBuN(H)CS(NMe2) H[L2] and MesN(H)CS(NMe2) H[L4] with either ZnMe2 (1:1) or Zn{N(SiMe3)2}2 (1:1 and 2:1) and characterised by elemental analysis, NMR spectroscopy and thermogravimetric analysis (TGA). The molecular structures of complexes [{L1}ZnMe]2 (1), [{L2}ZnMe]2] (2) [{L3}ZnMe]∞ (3), [{L4}ZnMe]2] (4), [{L1}Zn{N(SiMe3)2}]2 (5), [{L2}Zn{N(SiMe3)2}]2 (6), [{L3}Zn{N(SiMe3)2}]2] (7), [{L4}Zn{N(SiMe3)2}]2] (8), [{L1}2Zn]2 (9) and [{L4}2Zn]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 vapour 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 comprise 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 behaviour and band gap (Eg = 3.711-3.772 eV) values between those expected for bulk cubic-ZnS (Eg = 3.54 eV) and hexagonal-ZnS (Eg = 3.91 eV).
LanguageEnglish
JournalInorganic Chemistry
Early online date4 Feb 2019
DOIs
StatusE-pub ahead of print - 4 Feb 2019

Cite this

@article{7baa9ccb7b324b92b7a224af6f2ff896,
title = "Aerosol-Assisted Chemical Vapour Deposition of ZnS from Thioureide Single Source Precursors",
abstract = "A family of twelve Zinc(II) thoureide complexes, of the general form [{L}ZnMe], [{L}Zn{N(SiMe3)2}] and [{L}2Zn], have been synthesized by direct reaction of the thiourea pro-ligands iPrN(H)CS(NMe2) H[L1], CyN(H)CS(NMe2) H[L2], tBuN(H)CS(NMe2) H[L2] and MesN(H)CS(NMe2) H[L4] with either ZnMe2 (1:1) or Zn{N(SiMe3)2}2 (1:1 and 2:1) and characterised by elemental analysis, NMR spectroscopy and thermogravimetric analysis (TGA). The molecular structures of complexes [{L1}ZnMe]2 (1), [{L2}ZnMe]2] (2) [{L3}ZnMe]∞ (3), [{L4}ZnMe]2] (4), [{L1}Zn{N(SiMe3)2}]2 (5), [{L2}Zn{N(SiMe3)2}]2 (6), [{L3}Zn{N(SiMe3)2}]2] (7), [{L4}Zn{N(SiMe3)2}]2] (8), [{L1}2Zn]2 (9) and [{L4}2Zn]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 vapour 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 comprise 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 behaviour and band gap (Eg = 3.711-3.772 eV) values between those expected for bulk cubic-ZnS (Eg = 3.54 eV) and hexagonal-ZnS (Eg = 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 = "4",
doi = "10.1021/acs.inorgchem.8b03363",
language = "English",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",

}

TY - JOUR

T1 - Aerosol-Assisted Chemical Vapour 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 - 2019/2/4

Y1 - 2019/2/4

N2 - A family of twelve Zinc(II) thoureide complexes, of the general form [{L}ZnMe], [{L}Zn{N(SiMe3)2}] and [{L}2Zn], have been synthesized by direct reaction of the thiourea pro-ligands iPrN(H)CS(NMe2) H[L1], CyN(H)CS(NMe2) H[L2], tBuN(H)CS(NMe2) H[L2] and MesN(H)CS(NMe2) H[L4] with either ZnMe2 (1:1) or Zn{N(SiMe3)2}2 (1:1 and 2:1) and characterised by elemental analysis, NMR spectroscopy and thermogravimetric analysis (TGA). The molecular structures of complexes [{L1}ZnMe]2 (1), [{L2}ZnMe]2] (2) [{L3}ZnMe]∞ (3), [{L4}ZnMe]2] (4), [{L1}Zn{N(SiMe3)2}]2 (5), [{L2}Zn{N(SiMe3)2}]2 (6), [{L3}Zn{N(SiMe3)2}]2] (7), [{L4}Zn{N(SiMe3)2}]2] (8), [{L1}2Zn]2 (9) and [{L4}2Zn]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 vapour 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 comprise 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 behaviour and band gap (Eg = 3.711-3.772 eV) values between those expected for bulk cubic-ZnS (Eg = 3.54 eV) and hexagonal-ZnS (Eg = 3.91 eV).

AB - A family of twelve Zinc(II) thoureide complexes, of the general form [{L}ZnMe], [{L}Zn{N(SiMe3)2}] and [{L}2Zn], have been synthesized by direct reaction of the thiourea pro-ligands iPrN(H)CS(NMe2) H[L1], CyN(H)CS(NMe2) H[L2], tBuN(H)CS(NMe2) H[L2] and MesN(H)CS(NMe2) H[L4] with either ZnMe2 (1:1) or Zn{N(SiMe3)2}2 (1:1 and 2:1) and characterised by elemental analysis, NMR spectroscopy and thermogravimetric analysis (TGA). The molecular structures of complexes [{L1}ZnMe]2 (1), [{L2}ZnMe]2] (2) [{L3}ZnMe]∞ (3), [{L4}ZnMe]2] (4), [{L1}Zn{N(SiMe3)2}]2 (5), [{L2}Zn{N(SiMe3)2}]2 (6), [{L3}Zn{N(SiMe3)2}]2] (7), [{L4}Zn{N(SiMe3)2}]2] (8), [{L1}2Zn]2 (9) and [{L4}2Zn]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 vapour 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 comprise 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 behaviour and band gap (Eg = 3.711-3.772 eV) values between those expected for bulk cubic-ZnS (Eg = 3.54 eV) and hexagonal-ZnS (Eg = 3.91 eV).

U2 - 10.1021/acs.inorgchem.8b03363

DO - 10.1021/acs.inorgchem.8b03363

M3 - Article

JO - Inorganic Chemistry

T2 - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

ER -