Synthesis of Copper Sulphide-Based Hybrid Nanostructures and Their

CrystEngComm View Article Online HIGHLIGHT View Journal | View Issue Synthesis of copper sulphide-based hybrid nanostructures and their application in shape Cite this: CrystEngComm,2014,16, 9381 control of colloidal semiconductor nanocrystals Joanna Kolny-Olesiak Copper sulphide is a material with low toxicity and high application potential. Colloidal synthesis allows its incorporation into hybrid nanostructures, which not only combine the properties of different materials within one nanocrystal, but also exhibit new features due to the interaction of the building blocks connected on the nanometer scale. Starting with copper sulphide seeds, such hybrid nanocrystals Received 31st March 2014, composed of copper sulphide and semiconductors like CuInS2,CuInxGa1−xS2,Cu2ZnSnS4,ZnS,CdS,and Accepted 9th May 2014 PbS have been synthesized. In some of these reactions the main focus lies on the formation of new hybrid nanocrystals; in others copper sulphide plays the role of a catalyst, and copper sulphide containing hybrid DOI: 10.1039/c4ce00674g nanoparticles are only intermediates in the synthesis and shape control of other semiconductor materials. Creative Commons Attribution 3.0 Unported Licence. www.rsc.org/crystengcomm Both possibilities and the underlying growth mechanisms are discussed in this article. Introduction hexagonal or orthorhombic chalcocite Cu2S). Depending on the composition, the bandgap of Cu2−xS lies between 1.2 eV The field of nanochemistry rapidly evolved during the last (for Cu2S) and 2.0 eV (for CuS); thus, copper sulphide can two decades. Synthetic procedures have been developed which absorb a large fraction of the solar spectrum, which makes it allow for precise control of the size, shape, structure and com- an interesting material for photovoltaic applications. More- – position of a variety of nanostructured materials.1 8 These over, the large number of copper vacancies in the non- This article is licensed under a paved the way for studying the size and shape dependent stoichiometric compounds and the resulting high concentra- properties of nano-crystallites, and therefore, increased our tion of free charge carriers lead to plasmonic absorption in understanding of the properties of matter on the nanometer the IR spectral region.23 Furthermore, the presence of Open Access Article. Published on 12 May 2014. Downloaded 9/25/2021 8:16:01 PM. scale, resulting in possible creation of custom-made materials cationic vacancies and the high mobility of the cations facili- – for a variety of applications.9 12 The possibilities to manipulate tate incorporation of other cations into the copper sulphide and control the properties of nanocrystals can be greatly lattice. extended by generating nanoparticles composed of more than Because of these properties, copper sulphide is not only a one material. These so-called hybrid nanocrystals not only material with high application potential but also a suitable combine different optical, magnetic or catalytic features within catalyst which facilitates growth and enables shape control of – one nanostructure but also evolve with new characteristics.13 16 other semiconductor nanomaterials. Therefore, two aspects The focus of this article lies on the synthesis of will be discussed here: the possibility to modify the proper- semiconductor–semiconductor hybrid nanostructures which ties of copper sulphide particles by combining them with can be generated from copper sulphide seeds. Copper sulphide other semiconductors and the potential to synthesize shape- nanoparticles, which attract scientific attention due to their controlled nanocrystals in procedures including copper interesting properties, low toxicity and, therefore, high appli- sulphide containing intermediates. Recent advances in the cation potential, can be synthesized with a high degree of synthetic methods using copper sulphide seeds are summa- 17–22 control over their size and shape. Cu2−xS is a p-type semi- rized, and an overview of the current understanding of the conductor which can form several nonstoichiometric com- underlying reaction mechanisms is given. pounds with x ranging from 0 to 1 (hexagonal covellite CuS, orthorhombic anilite Cu1.75S, hexagonal digenite Cu1.8S, Overview of synthetic procedures monoclinic djurleite Cu1.94–1.97S, monoclinic roxbyite Cu1.75S, Several materials have already been combined with copper Energy and Semiconductor Research Laboratory, Department of Physics, Carl von 24–28 Ossietzky University of Oldenburg, 26129 Oldenburg, Germany. sulphide to form hybrid nanostructures, e.g.,CuInS2, 29,30 31,32 33–36 37 38 E-mail: [email protected]; Fax: +49 441 798 3326; CuInxGa1−xS2, Cu2ZnSnS4, ZnS, CdS, PbS, and 39 Tel: +49 441 798 3261 MnS. In all cases the synthetic procedures start with the This journal is © The Royal Society of Chemistry 2014 CrystEngComm,2014,16,9381–9390 | 9381 View Article Online Highlight CrystEngComm Table 1 Overview of synthetic methods to obtain copper sulphide based hybrid nanostructures Precursors, ligands, and solvents Method/conditions Shape, size, and structure Ref. Cu–In–S Cu-oleate, In-oleate, 230–250 °C, 10 min - 1 h, heat-up Acorn-shape: 30 nm × 48 nm, bottle-shape: 40 nm × 110 nm, Choi et al. OLAM, 1-DDT larva-shape: 45 nm × 185 nm 2006 (ref. 46) Cu(acac)2, In(acac)3, 1-DDT, 200 °C, injection of In(acac)3 into HNRs: 77 nm × 12.0 nm, tear-drops: 48 nm × 23 nm Han et al. preformed copper sulphide seeds 2008 (ref. 40) Cu-oleate, In-oleate, 215–300 °C, 20 min, heat-up Nanorods, WZ Connor et al. 1-DDT, OLAM 2009 (ref. 24) ° Cu(OAc)2, In(OAc)3, 240 C, 30 s - 1 h, hot-injection Various sizes, HNRs, P-shaped, hexagonal plates, WZ Kruszynska 1-DDT, t-DDT, TOPO, OLAM et al. 2010 (ref. 25) Cu(OAc)2, In(OAc)3, 1-DDT, 240 °C, 50 s - 1 h, hot-injection Triangular pyramids, WZ Kruszynska t-DDT, TOPO, ODE, OLAM et al. 2011 (ref. 27) Cu(NO3)2, In(NO3)3, 240°, 30 min, heat-up Quasi-spherical, rods, WZ Lu et al. 2011 1-DDT, OLAM, OA (ref. 28) Cu(dedc)2, Cu(acac)2, The mixture is rapidly heated to Nanoribbons with a rectangular cross-section: 2–3 μmin Li et al. 2013 ° – In(dedc)3, OLAM, 1-DDT 180 C by immersion in an oil length, 20 50 nm in width, 15 nm in thickness, WZ (ref. 29) bath, 60 min Cu–In–Zn–S ° – – – – CuOAc, In(OAc)3, zinc 240 C, slow precursor injection Various sizes, Cu2S ZnS, Cu2S CIS and Cu2S (CIS ZnS alloy) Chang and stearate, zinc ethylxanthate, via a syringe pump HNRs, chalcocite and WZ Cheng 2011 1-DDT, ODE (ref. 26) Cu1.94S–ZnS seeds, 200 °C, 4 h, heat-up Burning torch-like CIS–ZnS HNRs, head: 33 nm × 24 nm, tail: Yi et al. 2013 × In(OAc)3, 1-DDT, ODE 29 nm 9nm,WZ (ref. 47) Creative Commons Attribution 3.0 Unported Licence. 200 °C, 6 injections of In(ac)3, Long rod-like CIS–ZnS HNRs, WZ 4 h reaction after last injection Cu–Zn–S Cu(acac)2, Zn(acac)2, 1-DDT 200 °C, ca. 4–5 h, injection of HNRs Yi et al. 2010 Zn(acac)2 in 6 portions (ref. 33) CuI, Zn(dedt)2, OLAM 150 °C, 30 min, heat-up Hexagonal prism length: 60 nm; diameter: 30 nm, monoclinic Han et al. Cu1.94S, WZ ZnS 2012 (ref. 35) Cu-oleate, 1-DDT, OLAM 220 °C, 30 min, injection of 28 nm slab-like ZnS nanocrystals embedded in a Cu1.94Snano- Huang et al. ° Zn-oleate at 220 C sphere, monoclinic Cu1.94SandWZZnS 2012 (ref. 34) – ° Zn(acac)2, Cu(acac)2, 240 270 C, reaction times up to Taper-like, matchstick-like, tadpole-like, or rod-like hybrid Ye et al. 2013 1-DDT, ODE 360 min, heat-up nanostructures, monoclinic Cu S, WZ ZnS (ref. 36) This article is licensed under a 1.94 Cu–In–Ga–S Cu(acac)2, In(acac)3, Injection at 155 °C, reaction Nanorods, diameter: 7 nm, WZ Coughlan et al. – ° – Ga(acac)3, TOPO, ODE, temperature: 250 270 C, 15 30 min 2013 (ref. 30) 1-DDT, t-DDT Open Access Article. Published on 12 May 2014. Downloaded 9/25/2021 8:16:01 PM. – μ Cu(dedc)2, Cu(acac)2, The mixture is rapidly heated to Nanoribbons with a rectangular cross-section: 1 2 min Li et al. 2013 ° – In(dedc)3, Ga(dedc)3, 180 C by immersion in an oil length, 30 50 nm in width, 9 nm in thickness, variable (ref. 29) OLAM, 1-DDT bath, 60 min composition between 20 and 80% Ga, roxbyite and WZ Cu–Zn–Sn–S Cu(acac)2, Zn(OAc)2, SnCl2, 200–260 °C, different reaction Bullet-shape, 13 nm, WZ Liao et al. 1-DDT, OLAM, times: up to 24 h, heat-up 2013 (ref. 32) CuCl2, Zn(dedc)2, Sn(dedc)4, 200 °C, 60 min, fast heat-up by Nanorods, 200 nm in length, WZ Zhang et al. 1-DDT, OLAM immersion in an oil bath 2013 (ref. 31) Cu–Cd–Zn–S Cu(dedt)2, Cd(dedt)2, 250 °C, injection of Cd(dedt)2 Hexagonal discs with regions of monoclinic Cu1.94S and WZ Regulacio et al. Zn(dedt)2 hexanethiol, and Zn(dedt)2 into preformed CdS (CdxZn1-xS) 2011 (ref. 37) trioctylamine Cu1.94S seeds Cu–Pb–S Cu(acac)2, Pb(dedt)2, 200 °C, 10 min, injection of HNRs, chalcocite and rock salt Zhuang et al. 1-DDT Pb(dedt)2 into preformed Cu1.94S 2012 (ref. 38) seeds Cu–Mn–S ° Cu(OAc)2, Mn(OAc)2 220 C, 15 min, injection of HNRs, 16 nm in length, djurleite and WZ Zhou et al. 1-DDT, OLAM Mn(ac)2 into preformed Cu1.94S 2013 (ref. 39) seeds acac: acetylacetonate, dedt: diethyldithiocarbamate, 1-DDT: 1-dodecanethiol, t-DDT: tert-dodecanethiol, HDA: hexadecylamine, HNRs: hetero- structured nanorods, OA: oleic acid, OAc: acetate, ODE: octadecene, OLAM: oleylamine, TOPO: trioctylphosphine oxide, WZ: wurtzite, and ZB: zincblende.

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