journal article·2017-09Open access

Nickel sulfide thin films and nanocrystals synthesized from nickel xanthate precursors

Christine Buchmaier, Maximilian Glänzer, Ana Torvisco, Peter Poelt, Karin Wewerka, Birgit Kunert, Karl Gatterer, Gregor Trimmel, Thomas Rath

Journal of Materials Science· Volume 52· Issue 18

Abstract

Nickel sulfide thin films and nanocrystals stabilized with oleylamine ligands are prepared from two different nickel xanthates as single-source precursors, which decompose at approx. 180 °C, and are thereby converted into nickel sulfide. These nickel xanthates comprise branched alkyl moieties allowing the choice of a wide range of nonpolar organic solvents for the processing to nickel sulfide thin films as well as to nanoparticles. The crystal structures of both compounds show a typical square-planar coordination of the sulfur atoms of both xanthates to the nickel central atom. The thermal decomposition via the Chugaev reaction forming nickel sulfide was studied by thermal gravimetric analysis showing the reaction taking place at about 180 °C. Consequently, by thermally converting spin-coated metal xanthate films directly on the substrates in the solid state, thin films consisting of hexagonal nickel sulfide are formed. If the nickel xanthates are heated in an oleylamine solution, oleylamine-capped nickel sulfide nanocrystals are obtained, exhibiting hexagonal NiS as main phase and Ni 3 S 4 as secondary phase. This is also reflected in a sulfur-rich composition of the synthesized nickel sulfide nanocrystals as observed from TEM–EDX analyses.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Chalcogenide Semiconductor Thin Films · Quantum Dots Synthesis And Properties · Thermal and Kinetic Analysis

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (81)

Show source-provided references
1. Kullerud G, Yund RA (1962) The Ni-S system and related minerals. J Petrol 3:126–17510.1093/petrology/3.1.126 ↗
2. Wang X, Batter B, Xie Y, Pan K, Liao Y, Lv C, Li M, Sui S, Fu H (2015) Highly crystalline, small sized, monodisperse α-NiS nanocrystal ink as an efficient counter electrode for dye-sensitized solar cells. J Mater Chem A 3:15905–1591210.1039/C5TA02946E ↗
3. Idris NH, Rahman MM, Chou S-L, Wang J-Z, Wexler D, Liu H-K (2011) Rapid synthesis of binary α-NiS–β-NiS by microwave autoclave for rechargeable lithium batteries. Electrochim Acta 58:456–46210.1016/j.electacta.2011.09.066 ↗
4. Pan Y, Chen Y, Li X, Liu Y, Liu C (2015) Nanostructured nickel sulfides: phase evolution, characterization and electrocatalytic properties for the hydrogen evolution reaction. RSC Adv 5:104740–10474910.1039/C5RA18737K ↗
5. Pang H, Wei C, Li X, Li G, Ma Y, Li S, Chen J, Zhang J (2014) Microwave-assisted synthesis of NiS2 nanostructures for supercapacitors and cocatalytic enhancing photocatalytic H2 production. Sci Rep 4:357710.1038/srep03577 ↗
6. Liu Z, Zheng X, Luo S-L, Xu S-Q, Yuan N-Y, Ding J-N (2016) High performance Li–S battery based on amorphous NiS2 as the host material for the S cathode. J Mater Chem A 4:13395–1339910.1039/C6TA05635K ↗
7. Feng LL, Yu G, Wu Y, Li GD, Li H, Sun Y, Asefa T, Chen W, Zou X (2015) High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting. J Am Chem Soc 137:14023–1402610.1021/jacs.5b08186 ↗
8. Falkowski JM, Concannon NM, Yan B, Surendranath Y (2015) Heazlewoodite, Ni3S2: a potent catalyst for oxygen reduction to water under benign conditions. J Am Chem Soc 137:7978–798110.1021/jacs.5b03426 ↗
9. Zhang Y, Sun W, Rui X, Li B, Tan HT, Guo G, Madhavi S, Zong Y, Yan Q (2015) One-pot synthesis of tunable crystalline Ni3S4@amorphous MoS2 core/shell nanospheres for high-performance supercapacitors. Small 11:3694–370210.1002/smll.201403772 ↗
10. Gupta R, Fisher TS (2017) Scalable coating of single-source nickel hexadecanethiolate precursor on 3D graphitic petals for asymmetric supercapacitors. Energy Technol 5:740–746. doi: 10.1002/ente.20160047510.1002/ente.201600475 ↗
11. Ji S, Zhang L, Yu L, Xu X, Liu J (2016) In situ carbon-coating and Ostwald ripening-based route for hollow Ni3S4@C spheres with superior Li-ion storage performances. RSC Adv 6:101752–10175910.1039/C6RA21677C ↗
12. Cao F, Liu R, Zhou L, Song SY, Lei YQ, Shi WD, Zhao F, Zhang H (2010) One-pot synthesis of flowerlike Ni7S6 and its application in selective hydrogenation of chloronitrobenzene. J Mater Chem 20:1078–108510.1039/B916866D ↗
13. Wu W, Li Y, Jin J, Wu H, Wang S, Xia Q (2016) A novel nonenzymatic electrochemical sensor based on 3D flower-like Ni7S6 for hydrogen peroxide and glucose. Sens Actuator B Chem 232:633–64110.1016/j.snb.2016.04.006 ↗
14. Li H, Shao Y, Su Y, Gao Y, Wang X (2016) Vapor-phase atomic layer deposition of nickel sulfide and its application for efficient oxygen-evolution electrocatalysis. Chem Mater 28:1155–116410.1021/acs.chemmater.5b04645 ↗
15. Krishnakumar SR, Shanthi N, Sarma DD (2002) Electronic structure of millerite NiS. Phys Rev B 66:11510510.1103/PhysRevB.66.115105 ↗
16. Boughalmi R, Rahmani R, Boukhachem A, Amrani B, Driss-Khodja K, Amlouk M (2015) Metallic behavior of NiS thin film under the structural, optical, electrical and ab initio investigation frameworks. Mater Chem Phys 163:99–10610.1016/j.matchemphys.2015.07.019 ↗
17. Sparks JT, Komoto T (1967) Metal-to-semiconductor transition at the magnetic ordering temperature of NiS. Phys Lett A 25:398–39910.1016/0375-9601(67)90721-9 ↗
18. Sparks JT, Komoto T (1968) Metal-to-semiconductor transition in hexagonal NiS. Rev Mod Phys 40:752–75410.1103/RevModPhys.40.752 ↗
19. Kautz RL, Dresselhaus MS, Adler D, Linz A (1972) Electrical and optical properties of NiS2. Phys Rev B 6:2078–208210.1103/PhysRevB.6.2078 ↗
20. Metcalf PA, Crooker BC, McElfresh M, Kakol Z, Honig JM (1994) Low-temperature electronic and magnetic properties of single-crystal Ni3S2. Phys Rev B 50:2055–206010.1103/PhysRevB.50.2055 ↗
21. Parise JB (1980) Structure of hazelwoodite (Ni3S2). Acta Cryst B 36:1179–118010.1107/S0567740880005523 ↗
22. Manthiram A, Jeong YU (1999) Ambient temperature synthesis of spinel Ni3S4: an itinerant electron ferrimagnet. J Solid State Chem 147:679–68110.1006/jssc.1999.8492 ↗
23. Kulagov EA, Evstigneeva TL, Yushko-Zakharova OE (1969) The new nickel sulphide godlevskite. Geol Rudnykh Mestorozhderii 11:115–121
24. Bonneau PR, Shibao RK, Kaner RB (1990) Low-temperature precursor synthesis of crystalline nickel disulfide. Inorg Chem 29:2511–251410.1021/ic00338a024 ↗
25. An G, Chenguang L, Hou Y, Zhang X, Liu Y (2008) Transition metal dichalcogenide materials: solid-state reaction synthesis of nanocrystalline nickel disulfide. Mater Lett 62:2643–264610.1016/j.matlet.2008.01.005 ↗
26. Nozaki H, Aizawa T, Kosuda K (2005) Stabilized epitaxial films of hexagonal Ni1−xS on MgO(001). J Solid State Chem 178:2001–200710.1016/j.jssc.2005.04.009 ↗
27. Anischik VM, Markevich MI, Piskunov FA, Yanushkevich VA (1995) Pulsed-laser-induced synthesis of nickel sulphides in sulphur-containing liquids. Thin Solid Films 261:183–18510.1016/S0040-6090(94)06496-2 ↗
28. O’Brien P, Park JH, Waters J (2003) A single source approach to deposition of nickel sulfide thin films by LP-MOCVD. Thin Solid Films 431–432:502–50510.1016/S0040-6090(03)00244-X ↗
29. Chen X, Wang Z, Wang X, Wan J, Liu J, Qian Y (2004) A single-source approach to metastable Ni3S4 crystallites and their optical properties. Chem Lett 33:1294–129510.1246/cl.2004.1294 ↗
30. Hollingsworth N, Roffey A, Islam H-U, Mercy M, Roldan A, Bras W, Wolthers M, Catlow CRA, Sankar G, Hogarth G, de Leeuw NH (2014) Active nature of primary amines during thermal decomposition of nickel dithiocarbamates to nickel sulfide nanoparticles. Chem Mater 26:6281–629210.1021/cm503174z ↗
31. Prakasam BA, Lahtinen M, Peuronen A, Muruganandham M, Kolehmainen E, Haapaniemi E, Sillanpää M (2015) Spectral and structural studies on Ni(II) dithiocarbamates: nickel sulfide nanoparticles from a dithiocarbamate precursor. Inorg Chim Acta 425:239–24610.1016/j.ica.2014.09.016 ↗
32. Sathiyaraj E, Gurumoorthy G, Thirumaran S (2015) Nickel(II) dithiocarbamate complexes containing the pyrrole moiety for sensing anions and synthesis of nickel sulfide and nickel oxide nanoparticles. New J Chem 39:5336–534910.1039/C4NJ02250E ↗
33. Roffey A, Hollingsworth N, Islam H-U, Mercy M, Sankar G, Catlow CRA, Hogarth G, de Leeuw NH (2016) Phase control during the synthesis of nickel sulfide nanoparticles from dithiocarbamate precursors. Nanoscale 8:11067–1107510.1039/C6NR00053C ↗
34. Gervas C, Mlowe S, Akerman MP, Ezekiel I, Moyo T, Revaprasadu N (2017) Synthesis of rare pure phase Ni3S4 and Ni3S2 nanoparticles in different primary amine coordinating solvents. Polyhedron 122:16–2410.1016/j.poly.2016.11.014 ↗
35. Cheon J, Talaga DS, Zink JI (1997) Laser and thermal vapor deposition of metal sulfide (NiS, PdS) films and in situ gas-phase luminescence of photofragments from M(S2COCHMe2)2. Chem Mater 9:1208–121210.1021/cm960589u ↗
36. Pradhan N, Katz B, Efrima S (2003) Synthesis of high-quality metal sulfide nanoparticles from alkyl xanthate single precursors in alkylamine solvents. J Phys Chem B 107:13843–1385410.1021/jp035795l ↗
37. Alam N, Hill MS, Kociok-Köhn G, Zeller M, Mazhar M, Molloy KC (2008) Pyridine adducts of nickel(II) xanthates as single-source precursors for the aerosol-assisted chemical vapor deposition of nickel sulfide. Chem Mater 20:6157–616210.1021/cm801330v ↗
38. Barry L, Holmes JD, Otway DJ, Copley MP, Kazakova O, Morris MA (2010) Unusual magnetism in templated NiS nanoparticles. J Phys Condens Matter 22:07600110.1088/0953-8984/22/7/076001 ↗
39. Akhtar M, Revaprasadu N, Malik MA, Raftery J (2015) Deposition of phase pure nickel sulfide thin films from bis(O-alkylxanthato)–nickel(II) complexes by the aerosol assisted chemical vapour deposition (AACVD) method. Mater Sci Semicond Process 30:368–37510.1016/j.mssp.2014.10.023 ↗
40. Macreadie LK, Maynard-Casely HE, Batten SR, Turner DR, Chesman ASR (2015) Soluble xanthate compounds for the solution deposition of metal sulfide thin films. ChemPlusChem 80:107–11810.1002/cplu.201402110 ↗
41. Ghezelbash A, Sigman MB, Korgel BA (2004) Solventless synthesis of nickel sulfide nanorods and triangular nanoprisms. Nano Lett 4:537–54210.1021/nl035067+ ↗
42. Abboudi M, Mosset A (1994) Synthesis of d transition metal sulfides from amorphous dithiooxamide complexes. J Solid State Chem 109:70–7310.1006/jssc.1994.1073 ↗
43. Mgabi LP, Dladla BS, Malik MA, Garje SS, Akhtar J, Revaprasadu N (2014) Deposition of cobalt and nickel sulfide thin films from thio- and alkylthio-urea complexes as precursors via the aerosol assisted chemical vapour deposition technique. Thin Solid Films 564:51–5710.1016/j.tsf.2014.04.086 ↗
44. Tian L, Yep LY, Ong TT, Yi J, Ding J, Vittal JJ (2009) Synthesis of NiS and MnS nanocrystals from the molecular precursors (TMEDA)M(SC{O}C6H5)2 (M=Ni, Mn). Cryst Growth Des 9:352–35710.1021/cg800536w ↗
45. Abdelhady AL, Malik MA, O’Brien P, Tuna F (2012) Nickel and iron sulfide nanoparticles from thiobiurets. J Phys Chem C 116:2253–225910.1021/jp2078659 ↗
46. Geng B, Liu X, Ma J, Du Q (2007) A new nonhydrolytic single-precursor approach to surfactant-capped nanocrystals of transition metal sulphides. Mater Sci Eng B 145:17–2210.1016/j.mseb.2007.09.065 ↗
47. Sobhani A, Salavati-Niasari M (2013) Synthesis, characterization, optical and magnetic properties of a nickel sulfide series by three different methods. Superlattices Microstruct 59:1–1210.1016/j.spmi.2013.03.018 ↗
48. Beal JHL, Etchegoin PG, Tilley RD (2010) Transition metal polysulfide complexes as single-source precursors for metal sulfide nanocrystals. J Phys Chem C 114:3817–382110.1021/jp910354q ↗
49. Babashkina MG, Safin DA, Garcia Y (2012) Influence of the coordination mode in [Ni{RC(S)NP(S)(OiPr)2}2] for the formation of nickel-containing nanoparticles. Dalton Trans 41:2234–223610.1039/C1DT11755F ↗
50. Yadav R, Singh AK, Waghadkar Y, Kociok-Köhn G, Kumar A, Chauhan R, Rane S, Gosavi S (2017) 1,2-Bis(diphenylphosphino)ethane nickel(II) O, O’-dialkyldithiophosphates as potential precursors for nickel sulfides. New J Chem 41:1327–133310.1039/C6NJ03186B ↗
51. Rath T, Edler M, Haas W, Fischereder A, Moscher S, Schenk S, Trattnig R, Sezen M, Mauthner G, Pein A, Meischler D, Bartl K, Saf R, Bansal N, Haque SA, Hofer F, List EJW, Trimmel G (2011) A direct route towards polymer/copper indium sulfide nanocomposite solar cells. Adv Energy Mater 1:1046–105010.1002/aenm.201100442 ↗
52. Kaltenhauser V, Rath T, Haas W, Torvisco A, Müller SK, Friedel B, Kunert B, Saf R, Hofer F, Trimmel G (2013) Bismuth sulphide–polymer nanocomposites from a highly soluble bismuth xanthate precursor. J Mater Chem C 1:7825–783210.1039/c3tc31684j ↗
53. MacLachlan AJ, Rath T, Cappel UB, Dowland SA, Amenitsch H, Knall A-C, Buchmaier C, Trimmel G, Nelson J, Haque SA (2015) Polymer/nanocrystal hybrid solar cells: influence of molecular precursor design on film nanomorphology, charge generation and device performance. Adv Funct Mater 25:409–42010.1002/adfm.201403108 ↗
54. Rath T, MacLachlan AJ, Brown MD, Haque SA (2015) Structural, optical and charge generation properties of chalcostibite and tetrahedrite copper antimony sulfide thin films prepared from metal xanthates. J Mater Chem A 3:24155–2416210.1039/C5TA05777A ↗
55. Fischereder A, Schenk A, Rath T, Haas W, Delbos S, Gougaud C, Naghavi N, Pateter A, Saf R, Schenk D, Edler M, Bohnemann K, Reichmann A, Chernev B, Hofer F, Trimmel G (2013) Solution-processed copper zinc tin sulfide thin films from metal xanthate precursors. Monatsh Chem 144:273–28310.1007/s00706-012-0882-6 ↗
56. Tejos M, Rolón BG, del Río R, Cabello G (2008) CdS amorphous thin films photochemical synthesis and optical characterization. Mater Sci Semicond Process 11:94–9910.1016/j.mssp.2009.04.004 ↗
57. Rath T, Padeste C, Vockenhuber M, Fradler C, Edler M, Reichmann A, Letofsky-Papst I, Hofer F, Ekinci Y, Griesser T (2013) Direct extreme UV-lithographic conversion of metal xanthates into nanostructured metal sulfide layers for hybrid photovoltaics. J Mater Chem A 1:11135–1114010.1039/c3ta12592k ↗
58. Buchmaier C, Rath T, Pirolt F, Knall A-C, Kaschnitz P, Glatter O, Wewerka K, Hofer F, Kunert B, Krenn K, Trimmel G (2016) Room temperature synthesis of CuInS2 nanocrystals. RSC Adv 6:106120–10612910.1039/C6RA22813E ↗
59. Al-Shakban M, Xie Z, Savjani N, Malik MA, O’Brien P (2016) A facile method for the production of SnS thin films from melt reactions. J Mater Sci 51:6166–6172. doi: 10.1007/s10853-016-9906-710.1007/s10853-016-9906-7 ↗
60. Lewis EA, McNaughter PD, Yin Z, Chen Y, Brent JR, Saah SA, Raftery J, Awudza JAM, Malik MA, O’Brien P, Haigh SJ (2015) In situ synthesis of PbS nanocrystals in polymer thin films from lead(II) xanthate and dithiocarbamate complexes: evidence for size and morphology control. Chem Mater 27:2127–213610.1021/cm504765z ↗
61. MacLachlan AJ, O’Mahony FTF, Sudlow AL, Hill MS, Molloy KC, Nelson J, Haque SA (2014) Solution-processed mesoscopic Bi2S3:polymer photoactive layers. ChemPhysChem 15:1019–102310.1002/cphc.201301103 ↗
62. Gottlieb HE, Kotlyar V, Nudelman A (1997) NMR chemical shifts of common laboratory solvents as trace impurities. J Org Chem 62:7512–751510.1021/jo971176v ↗
63. Blessing RH (1995) An empirical correction for absorption anisotropy. Acta Cryst A 51:33–3810.1107/S0108767394005726 ↗
64. Sheldrick GM (1990) Phase annealing in SHELX-90: direct methods for larger structures. Acta Cryst A 46:467–47310.1107/S0108767390000277 ↗
65. Sheldrick GM (2015) SHELXT- Integrated space-group and crystal-structure determination. Acta Cryst A 71:3–810.1107/S2053273314026370 ↗
66. Spek AL (2003) Single-crystal structure validation with the program PLATON. J Appl Cryst 36:7–1310.1107/S0021889802022112 ↗
67. Müller P, Herbst-Irmer R, Spek A, Schneider T, Sawaya M (2006) Crystal structure refinement: a crystallographer’s guide to SHELXL. Oxford University Press, Oxford, p 56–9110.1093/acprof:oso/9780198570769.003.0005 ↗
68. Allen FH (2002) The Cambridge structural database: a quarter of a million crystal structures and rising. Acta Cryst B 58:380–38810.1107/S0108768102003890 ↗
69. Cox MJ, Tiekink ERT (1999) The crystal and molecular structures of some nickel(ll)bis(O-alkyldithiocarbonate)s and nickel(II)bis(N, N-dialkyldithiocarbamate)s: an evaluation of the coordination potential of 1,1-dithiolate ligands in their nickel(II) complexes. Z Kristallogr 214:242–25010.1524/zkri.1999.214.4.242 ↗
70. Husain A, Nami SAA, Singh SP, Oves M, Siddiqi KS (2011) Anagostic interactions, revisiting the crystal structure of nickel dithiocarbamate complex and its antibacterial and antifungal studies. Polyhedron 30:33–4010.1016/j.poly.2010.09.023 ↗
71. Singh SK, Drew MGB, Singh N (2013) Self assembly of homoleptic Ni(II) dithiocarbamates and dithiocarbimates via Ni···H–C anagostic and C-H···π (chelate) interactions. CrystEngComm 15:10255–1026510.1039/c3ce41358f ↗
72. Singh V, Chauhan R, Gupta AN, Kumar V, Drew MGB, Bahadur L, Singh N (2014) Photosensitizing activity of ferrocenyl bearing Ni(II) and Cu(II) dithiocarbamates in dye sensitized TiO2 solar cells. Dalton Trans 43:4752–476110.1039/c3dt52142g ↗
73. Gupta AN, Kumar V, Singh V, Manar KK, Drew MGB, Singh N (2014) Intermolecular anagostic interactions in group 10 metal dithiocarbamates. CrystEngComm 16:9299–930710.1039/C4CE01263A ↗
74. Kumar V, Singh V, Gupta AN, Singh SK, Drew MGB, Singh N (2015) Cooperative influence of ligand frameworks in sustaining supramolecular architectures of Ni(II)/Pd(II) heteroleptic dithio-dipyrrin complexes via non-covalent interactions. Polyhedron 89:304–31210.1016/j.poly.2015.01.020 ↗
75. Yadav MK, Rajput G, Prasad LB, Drew MGB, Singh N (2015) Rare intermolecular M···H–C anagostic interactions in homoleptic Ni(II)–Pd(II) dithiocarbamate complexes. New J Chem 39:5493–549910.1039/C5NJ00452G ↗
76. Sathiyaraj E, Selvaganapathi P, Thirumaran S, Ciattini S (2016) Synthesis, spectral, structural and computational studies on NiS4 and NiS2NP chromophores: anagostic and C–H···π (chelate) interactions in [Ni(dtc)(PPh3)(NCS)] (dtc=N-(2-phenylethyl)-N-(4-methoxybenzyl)- dithiocarbamate and N-(2-phenylethyl)-N-(4-chlorobenzyl)dithiocarbamate). J Mol Struct 1119:385–39510.1016/j.molstruc.2016.04.079 ↗
77. Brookhart M, Green MLH, Parkin G (2007) Agostic interactions in transition metal compounds. Proc Natl Acad Sci 104:6908–691410.1073/pnas.0610747104 ↗
78. Huynh HV, Wong LR, Ng PS (2008) Anagostic interactions and catalytic activities of sterically bulky benzannulated N-heterocyclic carbene complexes of nickel(II). Organometallics 27:2231–223710.1021/om800004j ↗
79. Okamura H, Naitoh J, Nanba T, Matoba M, Nishioka M, Anzai S, Shimoyama I, Fukui K, Miura H, Nakagawa H, Nakagawa K, Kinoshita T (1999) Optical study of the metal–nonmetal transition in Ni1-δS. Solid State Commun 112:91–9510.1016/S0038-1098(99)00277-X ↗
80. Pein A, Baghbanzadeh M, Rath T, Haas W, Maier E, Amenitsch H, Hofer F, Kappe CO, Trimmel G (2011) Investigation of the formation of CuInS2 nanoparticles by the oleylamine route: comparison of microwave-assisted and conventional syntheses. Inorg Chem 50:193–20010.1021/ic101651p ↗
81. Mourdikoudis S, Liz-Marzán LM (2013) Oleylamine in nanoparticle synthesis. Chem Mater 25:1465–147610.1021/cm4000476 ↗