Citation: Yong-Juan Lu, Jun-Hong Jia. The effect of complexing agent on crystal growth, structure and properties of nanostructured Cu_2-xS thin films[J]. Chinese Chemical Letters, ;2014, 25(11): 1473-1478. doi: 10.1016/j.cclet.2014.06.003 shu

The effect of complexing agent on crystal growth, structure and properties of nanostructured Cu_2-xS thin films

Yong-Juan Lu ^a,, ,
Jun-Hong Jia ^b,,

1.
a The School of Chemical Engineering, The Northwest University for Nationalities, Lanzhou 730030, China;
2.
b State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China

Corresponding author: Yong-Juan Lu, Jun-Hong Jia,
Received Date: 8 April 2014
Available Online: 28 May 2014

Thin films of Cu_2-xS (x=0, 1) were deposited on self-assembled, monolayer modified substrates in the copper-thiosulfate system with various concentrations of ethylene diamine tetraacetic acid (EDTA) at a low temperature of 70℃. The thin films were characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectroscope (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM). The optical and photoelectrochemical (PEC) properties of the Cu_2-xS semiconductor films were investigated by ultraviolet-visible (UV-vis) absorption spectroscopy and a three-electrode system. It is found that EDTA plays a key role in the process of Cu_2-xS nanocrystals formation and growth. The compositions of the Cu_2-xS nanocrystals varied from Cu₂S (chalcocide) to CuS (covellite) through adjusting the concentration of EDTA, which is used as a complexing agent to yield high-quality Cu_2-xS films. The growth mechanisms of Cu_2-xS nanocrystals with different EDTA concentrations are proposed and discussed in detail.
- Thin film,
- Chemical synthesis,
- Optical properties,
- Photoelectrochemical properties
1. [1]
  [1] D.C. Reynolds, G. Leies, L.L. Antes, R.E. Marburger, Photovoltaic effect in cadmium sulfide, Phys. Rev. 96 (1954) 533-534.
2. [2]
  [2] Y.B. Li, W. Lu, Q. Huang, et al., Copper sulfide nanoparticles for photothermal ablation of tumor cells, Nanomedicine 5 (2010) 1161-1171.
3. [3]
  [3] I. Ancutiene, V. Janickis, R. Ivanauskas, Formation and characterization of conductive thin layers of copper sulfide (CuxS) on the surface of polyethylene and polyamide by the use of higher polythionic acids, Appl. Surf. Sci. 252 (2006) 4218-4225.
4. [4]
  [4] Z.B. Hai, J.L. Huang, H. Remita, J.F. Chen, Enhancement of alternating current electroluminescence properties by the addition of graphene oxide nanosheets as dielectric materials, Mater. Lett. 108 (2013) 304-307.
5. [5]
  [5] M.T.S. Nair, L. Guerrero, P.K. Nair, Conversion of chemically deposited CuS thin films to Cu_1.8S and Cu_1.96S by annealing, Semicond. Sci. Technol. 13 (1998) 1164-1169.
6. [6]
  [6] C. Nunes de Carvalho, P. Parreira, et al., P-type CuxS thin films: integration in a thin film transistor structure, Thin Solid Films 543 (2013) 3-6.
7. [7]
  [7] H.T. Zhu, J.X. Wang, D.X. Wu, Fast synthesis, formation mechanism, and control of shell thickness of CuS hollow spheres, Inorg. Chem. 48 (2009) 7099-7104.
8. [8]
  [8] Y. Zhao, H. Pan, Y. Lou, et al., Plasmonic Cu_2-xS nanocrystals: optical and structural properties of copper-deficient copper(I) sulfides, J. Am. Chem. Soc. 131 (2009) 4253-4261.
9. [9]
  [9] P. Kumar, M. Gusain, R. Nagarajan, Synthesis of Cu_1.8S and CuS from copperthiourea containing precursors; anionic (Cl , NO3 , SO4 2 ) influence on the product stoichiometry, Inorg. Chem. 50 (2011) 3065-3070.
10. [10]
  [10] Q. Tian, M. Tang, Y. Sun, et al., Hydrophilic flower-like CuS superstructures as an efficient 980 nmlaser-driven photothermal agent for ablation of cancer cells, Adv. Mater. 23 (2011) 3542-3547.
11. [11]
  [11] N. Banerjee, S.B. Krupanidhi, Synthesis and structural characterization of two dimensional hierarchical covellite nano-structures, Mater. Chem. Phys. 137 (2012) 466-471.
12. [12]
  [12] S. Xu, Q. Wang, J.H. Cheng, Q.H. Meng, Y. Jiao, Preparation and characteristics of porous CuS microspheres consisted of polycrystalline nanoslices, Powder Technol. 199 (2010) 139-143.
13. [13]
  [13] M. Saranya, C. Santhosh, R. Ramachandran, et al., Hydrothermal growth of CuS nanostructures and its photocatalytic properties, Powder Technol. 252 (2014) 25-32.
14. [14]
  [14] J. Li, T.G. Jiu, G.H. Tao, et al., Manipulating surface ligands of copper sulfide nanocrystals: synthesis, characterization, and application to organic solar cells, J. Colloid Interface Sci. 419 (2014) 142-147.
15. [15]
  [15] M. Kemmler, M. Lazell, P. O'Brien, et al., The growth of thin films of copper chalcogenide films by MOCVD and AACVD using novel single-molecule precursors, J. Mater. Sci. Mater. Electron. 13 (2002) 531-535.
16. [16]
  [16] R. Kobayashi, T. Wada, S. Bakehe, R. Klenk, The effect of sulphur pressure on the depth distribution of elements in Cu(In,Ga)S2 films, Thin Solid Films 472 (2005) 71-75.
17. [17]
  [17] R. Cordova, H. Gomez, R. Schrebler, et al., Electrosynthesis and electrochemical characterization of a thin phase of CuxS (x! 2) on ITO electrode, Langmuir 18 (2002) 8647-8654.
18. [18]
  [18] M.T.S. Nair, P.K. Nair, Chemical bath deposition of CuxS thin films and their prospective large area applications, Semicond. Sci. Technol. 4 (1989) 191-199.
19. [19]
  [19] K.M. Gadave, C.D. Lokhande, Formation of CuxS films through a chemical bath deposition process, Thin Solid Films 229 (1993) 1-4.
20. [20]
  [20] T. Yamamoto, K. Tanaka, E. Kubota, K. Osakada, Deposition of copper sulfide on the surface of poly(ethylene terephthalate) and poly(vinyl alcohol) films in aqueous solution to give electrically conductive films Sxad, Chem. Mater. 5 (1993) 1352- 1357.
21. [21]
  [21] R.S. Mane, C.D. Lokhande, Chemical deposition method for metal chalcogenide thin films, Mater. Chem. Phys. 65 (2000) 1-31.
22. [22]
  [22] Z. Tao, T. Zhan, T. Zhou, X. Zhao, Z. Li, Synthesis, properties, and self-assembly of 2,3-bis(n-octyl) hexaazatriphenylene, Chin. Chem. Lett. 24 (2013) 453-456.
23. [23]
  [23] A.U. Ubale, Effect of complexing agent on growth process and properties of nanostructured Bi₂S₃ thin films deposited by chemical bath deposition method, Mater. Chem. Phys. 121 (2010) 555-560.
24. [24]
  [24] S.C. Liufu, L.D. Chen, Q. Yao, F.Q. Huang, In situ assembly of CuxS quantum-dots into thin film: a highly conductive p-type transparent film, J. Phys. Chem. C 112 (2008) 12085-12088.
25. [25]
  [25] S.R. Gadakh, C.H. Bhosale, Effect of concentration of complexing agent (tartaric acid) on the properties of spray deposited Sb₂S₃ thin films, Mater. Chem. Phys. 78 (2003) 367-371.
26. [26]
  [26] S.B. Patil, A.K. Singh, Effect of complexing agent on the photoelectrochemical properties of bath deposited CdS thin films, Appl. Surf. Sci. 256 (2010) 2884-2889.
27. [27]
  [27] K.W. Cheng, S.C. Wang, Effects of complex agents on the physical properties of Ag-In-S ternary semiconductor films using chemical bath deposition, Mater. Chem. Phys. 115 (2009) 14-20.
28. [28]
  [28] M.B. Sigman, A. Ghezelbash, T. Hanrath, et al., Solventless synthesis of monodisperse Cu₂S nanorods, nanodisks, and nanoplatelets, J. Am. Chem. Soc. 125 (2003) 16050-16057.
29. [29]
  [29] Y.J. Lu, X. Meng, G.W. Yi, J.H. Jia, In situ growth of CuS thin films on functionalized self-assembled monolayers using chemical bath deposition, J. Colloid Interface Sci. 356 (2011) 726-733.
30. [30]
  [30] N. Faucheux, R. Schweiss, K. Lutzow, C. Werner, T. Groth, Self-assembled monolayers with different terminating groups as model substrates for cell adhesion studies, Biomaterials 25 (2004) 2721-2730.
31. [31]
  [31] Y.H. Chen, C.Y. Huang, F.D. Lai, et al., Electroless deposition of the copper sulfide coating on polyacrylonitrile with a chelating agent of triethanolamine and its EMI shielding effectiveness, Thin Solid Films 517 (2009) 4984-4988.
32. [32]
  [32] M.D. Xin, K.W. Li, H. Wang, Synthesis of CuS thin films by microwave assisted chemical bath deposition, Appl. Surf. Sci. 256 (2009) 1436- 1442.
33. [33]
  [33] I. Grozdanov, C.K. Barlingay, S.K. Dey, M. Ristov, M. Najdoski, Experimental study of the copper thiosulfate system with respect to thin-film deposition, Thin Solid Films 250 (1994) 67-71.
34. [34]
  [34] S.V. Bagul, S.D. Chavhan, R. Sharma, Growth and characterization of CuxS (x=1.0, 1.76, and 2.0) thin films grown by solution growth technique (SGT), J. Phys. Chem. Solids 68 (2007) 1623-1629.
35. [35]
  [35] J.J. Nairn, P.J. Shapiro, B. Twamley, et al., Preparation of ultrafine chalcopyrite nanoparticles via the photochemical decomposition of molecular single-source precursors, Nano Lett. 6 (2006) 1218-1223.
36. [36]
  [36] D. Chen, Y.F. Gao, G. Wang, et al., Surface tailoring for controlled photoelectrochemical properties: effect of patterned TiO2 microarrays, J. Phys. Chem. C 111 (2007) 13163-13169.
37. [37]
  [37] E. Elizalde, F. Rueda, On minority-carrier transport parameter determination in heterojunctions from spectral response measurements: the cases of chalcocite, djurleite and digenite, J Phys. D: Appl. Phys. 19 (1986) 1563-1574.
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

The effect of complexing agent on crystal growth, structure and properties of nanostructured Cu2-xS thin films

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通讯作者: 陈斌, bchen63@163.com

The effect of complexing agent on crystal growth, structure and properties of nanostructured Cu_2-xS thin films