Deposition of SnS Thin Films from Sn(II) Thioamidate Precursors

Amanda Louise Catherall, Shasa Harris, Michael S. Hill, Andrew L. Johnson, Mary F. Mahon

Research output: Contribution to journalArticle

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Abstract

Two thioamide pro-ligands, R1N(H)C(S)R2 (R1 = t-Bu, R2 = i-Pr and R1 = i-Pr, R2 = i-Pr), were synthesized by treatment of the corresponding amides with Lawesson’s reagent. Reactions of [Sn{N(SiMe3)2}2] with two molar equivalents of 7 each thioamide pro-ligand yielded the tin(II) thioamidate species, bis(2-methyl-N-(1-methylethyl)-propanethioamide)tin(II) and bis[N-(1,1-dimethylethyl)-2-methylpropanethioamide]tin(II). Both of the new tin compounds have been characterized by 1H, 1C, and 119Sn NMR spectroscopy and elemental analysis. In addition, the solid-state structure of bis(2-methyl-N-(1-methylethyl)-10 propanethioamide)tin(II) has been determined through a single crystal X-ray diffraction analysis and shown to display a 11 monomeric constitution in which the tin(II) center occupies a distorted pseudosquare pyramidal geometry defined by the N2S2 donors and the stereochemically active lone pair. Both tin(II) derivatives have been assessed for their potential as single source precursors to SnS by TGA and by NMR spectroscopic analysis of the volatile organic products produced during their thermolysis. Both compounds have been utilized in the growth of thin films by aerosol-assisted chemical vapor deposition (AACVD). These latter studies provided film growth at temperatures as low as 200 °C. The films have been analyzed by pXRD, Raman spectroscopy, XPS, AFM, and SEM and are shown to comprise primarily the orthorhombic (Herzenbergite) phase of SnS, which is contaminated by only low levels of residual carbon (<5 at %). Although further films deposited onto Mo-coated substrates produced only limited photocurrents when illuminated, these results demonstrate the potential of such simple thioamidate derivatives to act as single source precursors to useful metal sulfide thin film materials.
LanguageEnglish
Pages5544-5551
JournalCrystal Growth and Design
Volume17
Issue number10
Early online date7 Sep 2017
DOIs
StatusPublished - 4 Oct 2017

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Tin
tin
Thin films
thin films
Thioamides
Tin Compounds
Tin compounds
Ligands
tin compounds
Derivatives
nuclear magnetic resonance
Thermolysis
ligands
Spectroscopic analysis
constitution
spectroscopic analysis
Sulfides
Film growth
Aerosols
Photocurrents

Keywords

  • Tin Sulfide
  • Thin Films
  • Single source precursors
  • Thioamidates

Cite this

Deposition of SnS Thin Films from Sn(II) Thioamidate Precursors. / Catherall, Amanda Louise; Harris, Shasa; Hill, Michael S.; Johnson, Andrew L.; Mahon, Mary F.

In: Crystal Growth and Design, Vol. 17, No. 10, 04.10.2017, p. 5544-5551.

Research output: Contribution to journalArticle

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title = "Deposition of SnS Thin Films from Sn(II) Thioamidate Precursors",
abstract = "Two thioamide pro-ligands, R1N(H)C(S)R2 (R1 = t-Bu, R2 = i-Pr and R1 = i-Pr, R2 = i-Pr), were synthesized by treatment of the corresponding amides with Lawesson’s reagent. Reactions of [Sn{N(SiMe3)2}2] with two molar equivalents of 7 each thioamide pro-ligand yielded the tin(II) thioamidate species, bis(2-methyl-N-(1-methylethyl)-propanethioamide)tin(II) and bis[N-(1,1-dimethylethyl)-2-methylpropanethioamide]tin(II). Both of the new tin compounds have been characterized by 1H, 1C, and 119Sn NMR spectroscopy and elemental analysis. In addition, the solid-state structure of bis(2-methyl-N-(1-methylethyl)-10 propanethioamide)tin(II) has been determined through a single crystal X-ray diffraction analysis and shown to display a 11 monomeric constitution in which the tin(II) center occupies a distorted pseudosquare pyramidal geometry defined by the N2S2 donors and the stereochemically active lone pair. Both tin(II) derivatives have been assessed for their potential as single source precursors to SnS by TGA and by NMR spectroscopic analysis of the volatile organic products produced during their thermolysis. Both compounds have been utilized in the growth of thin films by aerosol-assisted chemical vapor deposition (AACVD). These latter studies provided film growth at temperatures as low as 200 °C. The films have been analyzed by pXRD, Raman spectroscopy, XPS, AFM, and SEM and are shown to comprise primarily the orthorhombic (Herzenbergite) phase of SnS, which is contaminated by only low levels of residual carbon (<5 at {\%}). Although further films deposited onto Mo-coated substrates produced only limited photocurrents when illuminated, these results demonstrate the potential of such simple thioamidate derivatives to act as single source precursors to useful metal sulfide thin film materials.",
keywords = "Tin Sulfide, Thin Films , Single source precursors, Thioamidates",
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T1 - Deposition of SnS Thin Films from Sn(II) Thioamidate Precursors

AU - Catherall,Amanda Louise

AU - Harris,Shasa

AU - Hill,Michael S.

AU - Johnson,Andrew L.

AU - Mahon,Mary F.

PY - 2017/10/4

Y1 - 2017/10/4

N2 - Two thioamide pro-ligands, R1N(H)C(S)R2 (R1 = t-Bu, R2 = i-Pr and R1 = i-Pr, R2 = i-Pr), were synthesized by treatment of the corresponding amides with Lawesson’s reagent. Reactions of [Sn{N(SiMe3)2}2] with two molar equivalents of 7 each thioamide pro-ligand yielded the tin(II) thioamidate species, bis(2-methyl-N-(1-methylethyl)-propanethioamide)tin(II) and bis[N-(1,1-dimethylethyl)-2-methylpropanethioamide]tin(II). Both of the new tin compounds have been characterized by 1H, 1C, and 119Sn NMR spectroscopy and elemental analysis. In addition, the solid-state structure of bis(2-methyl-N-(1-methylethyl)-10 propanethioamide)tin(II) has been determined through a single crystal X-ray diffraction analysis and shown to display a 11 monomeric constitution in which the tin(II) center occupies a distorted pseudosquare pyramidal geometry defined by the N2S2 donors and the stereochemically active lone pair. Both tin(II) derivatives have been assessed for their potential as single source precursors to SnS by TGA and by NMR spectroscopic analysis of the volatile organic products produced during their thermolysis. Both compounds have been utilized in the growth of thin films by aerosol-assisted chemical vapor deposition (AACVD). These latter studies provided film growth at temperatures as low as 200 °C. The films have been analyzed by pXRD, Raman spectroscopy, XPS, AFM, and SEM and are shown to comprise primarily the orthorhombic (Herzenbergite) phase of SnS, which is contaminated by only low levels of residual carbon (<5 at %). Although further films deposited onto Mo-coated substrates produced only limited photocurrents when illuminated, these results demonstrate the potential of such simple thioamidate derivatives to act as single source precursors to useful metal sulfide thin film materials.

AB - Two thioamide pro-ligands, R1N(H)C(S)R2 (R1 = t-Bu, R2 = i-Pr and R1 = i-Pr, R2 = i-Pr), were synthesized by treatment of the corresponding amides with Lawesson’s reagent. Reactions of [Sn{N(SiMe3)2}2] with two molar equivalents of 7 each thioamide pro-ligand yielded the tin(II) thioamidate species, bis(2-methyl-N-(1-methylethyl)-propanethioamide)tin(II) and bis[N-(1,1-dimethylethyl)-2-methylpropanethioamide]tin(II). Both of the new tin compounds have been characterized by 1H, 1C, and 119Sn NMR spectroscopy and elemental analysis. In addition, the solid-state structure of bis(2-methyl-N-(1-methylethyl)-10 propanethioamide)tin(II) has been determined through a single crystal X-ray diffraction analysis and shown to display a 11 monomeric constitution in which the tin(II) center occupies a distorted pseudosquare pyramidal geometry defined by the N2S2 donors and the stereochemically active lone pair. Both tin(II) derivatives have been assessed for their potential as single source precursors to SnS by TGA and by NMR spectroscopic analysis of the volatile organic products produced during their thermolysis. Both compounds have been utilized in the growth of thin films by aerosol-assisted chemical vapor deposition (AACVD). These latter studies provided film growth at temperatures as low as 200 °C. The films have been analyzed by pXRD, Raman spectroscopy, XPS, AFM, and SEM and are shown to comprise primarily the orthorhombic (Herzenbergite) phase of SnS, which is contaminated by only low levels of residual carbon (<5 at %). Although further films deposited onto Mo-coated substrates produced only limited photocurrents when illuminated, these results demonstrate the potential of such simple thioamidate derivatives to act as single source precursors to useful metal sulfide thin film materials.

KW - Tin Sulfide

KW - Thin Films

KW - Single source precursors

KW - Thioamidates

UR - http://dx.doi.org/10.1021/acs.cgd.7b01100

U2 - 10.1021/acs.cgd.7b01100

DO - 10.1021/acs.cgd.7b01100

M3 - Article

VL - 17

SP - 5544

EP - 5551

JO - Crystal Growth and Design

T2 - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 10

ER -