Skip to main content
SpringerLink
Log in

Tailoring Shape and Crystallographic Phase of Copper Sulfide Nanostructures Using Novel Thiourea Complexes as Single Source Precursors

  • Published:
Journal of Inorganic and Organometallic Polymers and Materials Aims and scope Submit manuscript

Abstract

Copper sulfide thin films and nanoparticles have been prepared via aerosol assisted chemical vapour deposition and solvothermal hot injection routes, respectively. Both routes employed heterocyclic amine based benzoylthioureato-copper(II) complexes as single source precursors. Copper sulfide thin films of diverse morphologies ranging from cubic to snowy or irregular crystallites depending on the deposition temperature were observed. Powder X-ray diffraction studies of the as deposited thin films have indicated the formation of hexagonal and cubic phases of copper sulfide. In the case of the nanoparticles, Roxbyite (Cu1.75S) phase was obtained in dodecanethiol at temperatures of 150, 190 and 230 °C. However, a preferred growth of nanoparticles was observed in the presence of oleylamine whereas the roxbyite phase was obtained at temperatures of 150, 200 and 250 °C. Also transmission electron microscopy showed the formation of close to spherical, hexagonal nano-disk and rod shaped nanoparticles.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. B. Srinivas, B.G. Kumar, K. Muralidharan, Stabilizer free copper sulphide nanostructures for rapid photocatalytic decomposition of rhodamine B. J. Mol. Catal. Chem. 410, 8–18 (2015)

    Article  CAS  Google Scholar 

  2. H. Lei, P. Qin, W. Ke, Y. Guo, X. Dai, Z. Chen et al., Performance enhancement of polymer solar cells with high work function CuS modified ITO as anodes. Org. Electron. 22, 173–179 (2015)

    Article  CAS  Google Scholar 

  3. A.A. Sagade, R. Sharma, Copper sulphide (CuxS) as an ammonia gas sensor working at room temperature. Sens. Actuators B 133, 135–143 (2008)

    Article  CAS  Google Scholar 

  4. M. Zhou, N. Peng, Z. Liu, Y. Xi, H. He, Y. Xia, Z. Liu, S. Okada, Synthesis of sub-10 nm copper sulfide rods as high-performance anode for long-cycle life Li-ion batteries. J. Power Sources 306, 408–412 (2016)

    Article  CAS  Google Scholar 

  5. Y.-K. Hsu, Y.-C. Chen, Y.-G. Lin, Synthesis of copper sulfide nanowire arrays for high-performance supercapacitors. Electrochim. Acta 139, 401–407 (2014)

    Article  CAS  Google Scholar 

  6. B. Mulder, Optical properties of crystals of cuprous sulphides (chalcosite, djurleite, Cu1. 9S, and digenite. Phys. Status Solidi A 13, 79–88 (1972)

    Article  CAS  Google Scholar 

  7. Y. Wu, C. Wadia, W. Ma, B. Sadtler, A.P. Alivisatos, Synthesis and photovoltaic application of copper(I) sulfide nanocrystals. Nano Lett. 8, 2551–2555 (2008)

    Article  CAS  PubMed  Google Scholar 

  8. M. Lotfipour, T. Machani, D.P. Rossi, K.E. Plass, α-Chalcocite nanoparticle synthesis and stability. Chem. Mater. 23, 3032–3038 (2011)

    Article  CAS  Google Scholar 

  9. Q. Tian, F. Jiang, R. Zou, Q. Liu, Z. Chen, M. Zhu et al., Hydrophilic Cu9S5 nanocrystals: a photothermal agent with a 25.7% heat conversion efficiency for photothermal ablation of cancer cells in vivo. ACS Nano 5, 9761–9771 (2011)

    Article  CAS  PubMed  Google Scholar 

  10. G. Song, L. Han, W. Zou, Z. Xiao, X. Huang, Z. Qin et al., A novel photothermal nanocrystals of Cu7S4 hollow structure for efficient ablation of cancer cells. Nano–Micro Lett. 6, 169–177 (2014)

    CAS  Google Scholar 

  11. Y. Takano, N. Uchiyama, S. Ogawa, N. Môri, Y. Kimishima, S. Arisawa et al., Superconducting properties of CuS2– xSex under high pressure. Physica C 341, 739–740 (2000)

    Article  Google Scholar 

  12. M.D. Khan, M.A. Malik, J. Akhtar, S. Mlowe, N. Revaprasadu, Phase pure deposition of flower-like thin films by aerosol assisted chemical vapor deposition and solvent mediated structural transformation in copper sulfide nanostructures. Thin Solid Films 638, 338–344 (2017)

    Article  CAS  Google Scholar 

  13. A.L. Abdelhady, K. Ramasamy, M.A. Malik, P. O’Brien, S.J. Haigh, J. Raftery, New routes to copper sulfide nanostructures and thin films. J. Mater. Chem. 21, 17888–17895 (2011)

    Article  CAS  Google Scholar 

  14. W.P. Lim, C.T. Wong, S.L. Ang, H.Y. Low, W.S. Chin, Phase-selective synthesis of copper sulfide nanocrystals. Chem. Mater. 18, 6170–6177 (2006)

    Article  CAS  Google Scholar 

  15. M.D. Khan, M. Akhtar, M.A. Malik, N. Revaprasadu, P. O’Brien, New examples of phase control in the preparation of copper sulfide nanoparticles and deposition of thin films by AACVD from bis (piperidinedithiocarbamato) copper(II) complex. ChemistrySelect 3, 2943–2950 (2018)

    Article  CAS  Google Scholar 

  16. X.-S. Du, Z.-Z. Yu, A. Dasari, J. Ma, Y.-Z. Meng, Y.-W. Mai, Facile synthesis and assembly of Cu2S nanodisks to corncoblike nanostructures. Chem. Mater. 18, 5156–5158 (2006)

    Article  CAS  Google Scholar 

  17. S. Li, H. Wang, W. Xu, H. Si, X. Tao, S. Lou et al., Synthesis and assembly of monodisperse spherical Cu2S nanocrystals. J. Colloid Interface Sci. 330, 483–487 (2009)

    Article  CAS  PubMed  Google Scholar 

  18. W. Lou, M. Chen, X. Wang, W. Liu, Size control of monodisperse copper sulfide faceted nanocrystals and triangular nanoplates. J. Phys. Chem. C 111, 9658–9663 (2007)

    Article  CAS  Google Scholar 

  19. J.M. Luther, H. Zheng, B. Sadtler, A.P. Alivisatos, Synthesis of PbS nanorods and other ionic nanocrystals of complex morphology by sequential cation exchange reactions. J. Am. Chem. Soc. 131, 16851–16857 (2009)

    Article  CAS  PubMed  Google Scholar 

  20. Y. Wang, Y. Hu, Q. Zhang, J. Ge, Z. Lu, Y. Hou et al., One-pot synthesis and optical property of copper(I) sulfide nanodisks. Inorg. Chem. 49, 6601–6608 (2010)

    Article  CAS  PubMed  Google Scholar 

  21. L. Chen, Y.-B. Chen, L.-M. Wu, Synthesis of uniform Cu2S nanowires from copper – thiolate polymer precursors by a solventless thermolytic method. J. Am. Chem. Soc. 126, 16334–16335 (2004)

    Article  CAS  PubMed  Google Scholar 

  22. M.D. Khan, J. Akhtar, M.A. Malik, N. Revaprasadu, Tuning the phase and shape of copper sulfide nanostructures using mixed solvent systems. ChemistrySelect 1, 5982–5989 (2016)

    Article  CAS  Google Scholar 

  23. M. Al-Shakban, P.D. Matthews, G. Deogratias, P.D. McNaughter, J. Raftery, I. Vitorica-Yrezabal et al., Novel xanthate complexes for the size-controlled synthesis of copper sulfide nanorods. Inorg. Chem. 56, 9247–9254 (2017)

    Article  CAS  PubMed  Google Scholar 

  24. H.-T. Zhang, G. Wu, X.-H. Chen, Large-scale synthesis and self-assembly of monodisperse hexagon Cu2S nanoplates. Langmuir 21, 4281–4282 (2005)

    Article  CAS  PubMed  Google Scholar 

  25. H. Zhang, G. Wu, X. Chen, Controlled synthesis and characterization of covellite (CuS) nanoflakes. Mater. Chem. Phys. 98, 298–303 (2006)

    Article  CAS  Google Scholar 

  26. I. Jen-La Plante, T.W. Zeid, P. Yang, T. Mokari, Synthesis of metal sulfide nanomaterials via thermal decomposition of single-source precursors. J. Mater. Chem. 20, 6612–6617 (2010)

    Article  CAS  Google Scholar 

  27. A. Ghezelbash, B.A. Korgel, Nickel sulfide and copper sulfide nanocrystal synthesis and polymorphism. Langmuir 21, 9451–9456 (2005)

    Article  CAS  PubMed  Google Scholar 

  28. A. Tang, S. Qu, K. Li, Y. Hou, F. Teng, J. Cao et al., One-pot synthesis and self-assembly of colloidal copper(I) sulfide nanocrystals. Nanotechnology 21, 285602 (2010)

    Article  CAS  PubMed  Google Scholar 

  29. S.-Y. Wang, W. Wang, Z.-H. Lu, Asynchronous-pulse ultrasonic spray pyrolysis deposition of CuxS (x = 1, 2) thin films. Mater. Sci. Eng. B 103, 184–188 (2003)

    Article  CAS  Google Scholar 

  30. S. Sartale, C. Lokhande, Growth of copper sulphide thin films by successive ionic layer adsorption and reaction (SILAR) method. Mater. Chem. Phys. 65, 63–67 (2000)

    Article  CAS  Google Scholar 

  31. H. Hu, P. Nair, Electrical and optical properties of poly (methyl methacrylate) sheets coated with chemically deposited CuS thin films. Surf. Coat. Technol. 81, 183–189 (1996)

    Article  CAS  Google Scholar 

  32. A.A. Memon, M. Dilshad, N. Revaprasadu, M.A. Malik, J. Raftery, J. Akhtar, Deposition of cadmium sulfide and zinc sulfide thin films by aerosol-assisted chemical vapors from molecular precursors. Turk. J. Chem. 39, 169–178 (2015)

    Article  CAS  Google Scholar 

  33. T. Trindade, P. O’Brien, Synthesis of CdS and CdSe nanoparticles by thermolysis of diethyldithio-or diethyldiseleno-carbamates of cadmium. J. Mater. Chem. 6, 343–347 (1996)

    Article  CAS  Google Scholar 

  34. N. Moloto, N. Revaprasadu, M. Moloto, P. O’Brien, M. Helliwell, N, N′-Diisopropyl-and N, N′-dicyclohexylthiourea cadmium(II) complexes as precursors for the synthesis of CdS nanoparticles. Polyhedron 26, 3947–3955 (2007)

    Article  CAS  Google Scholar 

  35. M. Lazell, S.J. Nørager, P. O’Brien, N. Revaprasadu, The use of dithio-and diselenocarbamates as precursors to nanoscale materials. Mater. Sci. Eng. C 16, 129–133 (2001)

    Article  Google Scholar 

  36. M. Afzaal, D. Crouch, M.A. Malik, M. Motevalli, P. O’Brien, J.H. Park et al., Deposition of II-VI thin films by LP-MOCVD using novel single-source precursors. Eur. J. Inorg. Chem. 2004, 171–177 (2004)

    Article  CAS  Google Scholar 

  37. C.Q. Nguyen, A. Adeogun, M. Afzaal, M.A. Malik, P. O’Brien, Facile and reproducible syntheses of bis (dialkylselenophosphenyl)-selenides and-diselenides: X-ray structures of (i Pr2PSe)2Se,(i Pr2PSe)2Se2 and (Ph2PSe)2Se. Chem. Commun. 20, 2179–2181 (2006)

    Article  CAS  Google Scholar 

  38. T. Alqahtani, M.D. Khan, D.J. Kelly, S.J. Haigh, D.J. Lewis, P. O’Brien, Synthesis of Bi2– 2x Sb2xS3 (0 ≤ x ≤ 1) solid solutions from solventless thermolysis of metal xanthate precursors. J. Mater. Chem. C. 6, 12652–12659 (2018)

    Article  Google Scholar 

  39. M.D. Khan, G. Murtaza, N. Revaprasadu, P. O’Brien, Synthesis of chalcopyrite-type and thiospinel minerals/materials by low temperature melts of xanthates. Dalton Trans. 47, 8870–8873 (2018)

    Article  CAS  PubMed  Google Scholar 

  40. K.I. Ketchemen, S. Mlowe, L.D. Nyamen, A.A. Aboud, M.P. Akerman, P.T. Ndifon et al., Heterocyclic lead(II) thioureato complexes as single-source precursors for the aerosol assisted chemical vapour deposition of PbS thin films. Inorg. Chim. Acta 479, 42–48 (2018)

    Article  CAS  Google Scholar 

  41. M.D. Khan, S. Hameed, N. Haider, A. Afzal, M.C. Sportelli, N. Cioffi et al., Deposition of morphology-tailored PbS thin films by surfactant-enhanced aerosol assisted chemical vapor deposition. Mater. Sci. Semicond. Process. 46, 39–45 (2016)

    Article  CAS  Google Scholar 

  42. H. Arslan, N. Külcü, U. Flörke, Synthesis and characterization of copper(II), nickel(II) and cobalt(II) complexes with novel thiourea derivatives. Transit. Met. Chem. 28, 816–819 (2003)

    Article  CAS  Google Scholar 

  43. M. Mikami, I. Nakagawa, T. Shimanouchi, Far infra-red spectra and metal—ligand force constants of acetylacetonates of transition metals. Spectrochim. Acta A 23, 1037–1053 (1967)

    Article  Google Scholar 

  44. M. Merdivan, F. Karipcin, N. Kulcu, R. Aygun, Study of the thermal decompositions on N, N-dialkyl-N’-benzoylthiourea complexes of Cu(II), Ni(II), Pd(II), Pt(II), Cd(II), Ru(III) and Fe(III). J. Ther. Anal. Calorim. 58, 551–557 (1999)

    Article  CAS  Google Scholar 

  45. N. Mntungwa, M. Khan, S. Mlowe, N. Revaprasadu, A simple route to alkylamine capped antimony nanoparticles. Mater. Lett. 145, 239–242 (2015)

    Article  CAS  Google Scholar 

  46. M.D. Khan, J. Akhtar, M.A. Malik, M. Akhtar, N. Revaprasadu, Phase-pure fabrication and shape evolution studies of SnS nanosheets. New J. Chem. 39, 9569–9574 (2015)

    Article  CAS  Google Scholar 

  47. M.D. Khan, M. Aamir, M. Sohail, M. Sher, J. Akhtar, M.A. Malik et al., Novel single source precursor for synthesis of Sb2Se3 nanorods and deposition of thin films by AACVD: photo-electrochemical study for water reduction catalysis. Sol. Energy 169, 526–534 (2018)

    Article  CAS  Google Scholar 

  48. M.D. Khan, M. Aamir, G. Murtaza, M.A. Malik, N. Revaprasadu, Structural investigations of SnS1– xSex solid solution synthesized from chalcogeno-carboxylate complexes of organo-tin by colloidal and solvent-less routes. Dalton Trans. 47, 10025–10034 (2018)

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

The authors thank the Royal Society/Department for International Development (RS-DFID) Africa Capacity Building Initiative programme and the National Research Foundation (NRF) South Africa through the South African Research Chair Initiative (SARChI) for their financial support. The authors also acknowledge the University of Kwa-Zulu Natal for TEM analyses.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Zululand, Private Bag X1001, Kwadlangezwa, 3880, South Africa

    Kevin I. Y. Ketchemen, Malik D. Khan, Sixberth Mlowe & Neerish Revaprasadu

  2. Department of Inorganic Chemistry, University of Yaoundé I, P.O. Box 812, Yaoundé, Cameroon

    Kevin I. Y. Ketchemen, Linda D. Nyamen & Peter T. Ndifon

  3. School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK

    Kevin I. Y. Ketchemen & Paul O’Brien

  4. School of Materials, University of Manchester, Oxford Road, Manchester, M13 9PL, UK

    Paul O’Brien

Authors
  1. Kevin I. Y. Ketchemen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Malik D. Khan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Sixberth Mlowe
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Linda D. Nyamen
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Peter T. Ndifon
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Paul O’Brien
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Neerish Revaprasadu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Peter T. Ndifon or Neerish Revaprasadu.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 437 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ketchemen, K.I.Y., Khan, M.D., Mlowe, S. et al. Tailoring Shape and Crystallographic Phase of Copper Sulfide Nanostructures Using Novel Thiourea Complexes as Single Source Precursors. J Inorg Organomet Polym 29, 917–927 (2019). https://doi.org/10.1007/s10904-018-01066-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10904-018-01066-z

Keywords

Search

Navigation