The University of Southampton
University of Southampton Institutional Repository

Chalcogenoether complexes of Nb(V) thio- and seleno-halides as single source precursors for low pressure chemical vapour deposition of NbS2 and NbSe2 thin films

Chalcogenoether complexes of Nb(V) thio- and seleno-halides as single source precursors for low pressure chemical vapour deposition of NbS2 and NbSe2 thin films
Chalcogenoether complexes of Nb(V) thio- and seleno-halides as single source precursors for low pressure chemical vapour deposition of NbS2 and NbSe2 thin films
NbSCl3 was obtained via reaction of NbCl5 with S(SiMe3)2 in anhydrous CH2Cl2, whilst in MeCN solution the same reaction gives [NbSCl3(MeCN)2]. [NbSeCl3(MeCN)2] was obtained similarly from NbCl5 with Se(SiMe3)2. The chalcogenoether complexes, [NbSCl3(ER2)] (E = S: R = Me, nBu; E = Se: R = nBu), were obtained from reaction of NbCl5, ER2 and S(SiMe3)2 in CH2Cl2. The structure of the [Nb2S2Cl6(SMe2)2] reveals a Cl-bridged dimer with the SMe2 ligands disposed syn. The Cl bridges are highly asymmetric, with the long Nb–Cl bond trans Nb[double bond, length as m-dash]S. The complexes, [NbSCl3(L–L)] (L–L = MeSCH2CH2SMe, MeS(CH2)3SMe, iPrSCH2CH2SiPr, MeSe(CH2)3SeMe and nBuS(CH2)3SnBu), were obtained from reaction of L–L with preformed [NbSCl3(MeCN)2]. The structures of the Me-substituted complexes reveal distorted octahedral monomers with the neutral ligands trans to S/Cl. Solution 1H and 77Se{1H} NMR data showed that the neutral ligands are partially dissociated and undergoing fast exchange at ambient temperatures in CH2Cl2 solution, consistent with weak Lewis acidity for NbSCl3. The complexes containing nBu-substituted ligands have been used as single source precursors for low pressure chemical vapour deposition (CVD) of 3R-NbS2 thin films. 2H-NbSe2 thin films were also obtained via low pressure CVD using [NbSe2Cl3(SenBu2)]. The thin films were characterised by grazing incidence and in-plane XRD, pole figure analysis, scanning electron microscopy and energy dispersive X-ray analysis.
0300-9246
Chang, Yao-Pang
9516eba3-1424-411c-8f13-c564cae63407
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Chang, Yao-Pang
9516eba3-1424-411c-8f13-c564cae63407
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Chang, Yao-Pang, Hector, Andrew L., Levason, William and Reid, Gillian (2017) Chalcogenoether complexes of Nb(V) thio- and seleno-halides as single source precursors for low pressure chemical vapour deposition of NbS2 and NbSe2 thin films. Dalton Transactions. (doi:10.1039/C7DT01911D).

Record type: Article

Abstract

NbSCl3 was obtained via reaction of NbCl5 with S(SiMe3)2 in anhydrous CH2Cl2, whilst in MeCN solution the same reaction gives [NbSCl3(MeCN)2]. [NbSeCl3(MeCN)2] was obtained similarly from NbCl5 with Se(SiMe3)2. The chalcogenoether complexes, [NbSCl3(ER2)] (E = S: R = Me, nBu; E = Se: R = nBu), were obtained from reaction of NbCl5, ER2 and S(SiMe3)2 in CH2Cl2. The structure of the [Nb2S2Cl6(SMe2)2] reveals a Cl-bridged dimer with the SMe2 ligands disposed syn. The Cl bridges are highly asymmetric, with the long Nb–Cl bond trans Nb[double bond, length as m-dash]S. The complexes, [NbSCl3(L–L)] (L–L = MeSCH2CH2SMe, MeS(CH2)3SMe, iPrSCH2CH2SiPr, MeSe(CH2)3SeMe and nBuS(CH2)3SnBu), were obtained from reaction of L–L with preformed [NbSCl3(MeCN)2]. The structures of the Me-substituted complexes reveal distorted octahedral monomers with the neutral ligands trans to S/Cl. Solution 1H and 77Se{1H} NMR data showed that the neutral ligands are partially dissociated and undergoing fast exchange at ambient temperatures in CH2Cl2 solution, consistent with weak Lewis acidity for NbSCl3. The complexes containing nBu-substituted ligands have been used as single source precursors for low pressure chemical vapour deposition (CVD) of 3R-NbS2 thin films. 2H-NbSe2 thin films were also obtained via low pressure CVD using [NbSe2Cl3(SenBu2)]. The thin films were characterised by grazing incidence and in-plane XRD, pole figure analysis, scanning electron microscopy and energy dispersive X-ray analysis.

Text
NbSCl3_final_revised_24_06_2017 - Accepted Manuscript
Download (1MB)

More information

Accepted/In Press date: 26 June 2017
e-pub ahead of print date: 26 June 2017

Identifiers

Local EPrints ID: 412688
URI: https://eprints.soton.ac.uk/id/eprint/412688
ISSN: 0300-9246
PURE UUID: 9560f1ed-4fa0-460b-bb5b-c8139da4a9fa
ORCID for Andrew L. Hector: ORCID iD orcid.org/0000-0002-9964-2163
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 26 Jul 2017 16:30
Last modified: 15 Oct 2019 04:52

Export record

Altmetrics

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of https://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×