Solvothermal Preparation and Growth Mechanism of CuInS2 Thin Films of Nanosheet Array

doi:10.7503/cjcu20140235

Abstract

Abstract:

CuInS₂(CIS) thin films of nanosheet array were deposited directly onto transparent conductive fluorine-doped tin oxide(FTO) substrates by solvothermal method using the precursors of copper(Ⅱ) chloride dihydrate, indium(Ⅲ) nitrate, thiourea, hexadecyl trimethyl ammonium bromide, oxalic acid, and ethanol. The morphology, crystallographic structure, chemical composition, and optical property of CIS thin films of nanosheet array were investigated using scanning electron microscopy(SEM), high resolution transmission electron microscopy(HRTEM), X-ray diffraction(XRD), Raman spectrum, energy dispersive spectrometry(EDS) and UV-Vis spectroscopy, respectively. It is revealed that highly uniform and dense vertical arrays of single crystalline nanosheets with chalcopyrite planes are formed. The atomic ratio of Cu/In/S is 1.1:1:2.09, very close to theoretical value of 1:1:2 of stoichiometric CIS. CIS thin films of nanosheet array have good light absorption characteristics at the UV-visible and near infrared wave range, and the optical band gap is found to be 1.51 eV. The growth mechanism of CIS thin films of nanosheet array was investigated according to the characterization of CIS thin films deposited at different reaction times.

Key words: Solvothermal synthesis, CuInS2, Nanosheet array, Growth mechanism

CLC Number:

O611

TrendMD:

ZHUANG Mixue, WEI Aixiang, LIU Jun, YAN Zhiqiang, ZHAO Yu. Solvothermal Preparation and Growth Mechanism of CuInS₂ Thin Films of Nanosheet Array[J]. Chem. J. Chinese Universities, 2014, 35(11): 2310.

Figures/Tables 6

Fig.1 SEM images of vertically oriented CIS thin film of nanosheet array grown on FTO coated glass (A, B) Top-view; (C) cross-sectional view.

Fig.2 XRD pattern(A), Raman spectrum(B) and HRTEM images(C, D) of CIS thin film of nanosheet array Inset in (D) is the enlarged HRTEM image of the same nanosheet array.

Fig.3 Reflection(A) and transmission(B) spectra and (αhν)2-hν curve(C) of CIS thin film of nanosheet array

Fig.4 SEM images of FTO substrate(A) and thin films of CIS nanosheet array grown on FTO substrate with growth time of 20 min(B), 40 min(C), 1 h(D, G), 4 h(E, H) and 8 h(F, I) (A—F) Top view; (G—I) cross-section view.

Fig.5 XRD patterns of CIS thin films of nanosheet array(A) and powders(B) synthesized in reaction solution Reaction time/h: (A) a. 1, b. 4, c. 8, d. 14, e. 20; (B) a. 0, b. 1, c. 4, d. 8, e. 14, f. 20.

Table 1 Content of elements in the CIS thin films of nanosheet array and powders synthesized in reaction solution

Sample	Reaction time/h	Atomic fraction(%)			n(Cu):n(In):n(S)
Sample	Reaction time/h	Cu	In	S	n(Cu):n(In):n(S)
CIS thin film	4	12.24	30.90	56.86	0.40:1:1.84
	8	14.64	30.13	55.23	0.49:1:1.83
	14	26.21	23.84	49.95	1.10:1:2.09
	20	27.69	22.88	49.42	1.21:1:2.16
CIS powder	1	43.00	14.46	42.54	2.97:1:2.94
	4	29.40	18.13	52.47	1.62:1:2.89
	8	27.82	20.40	51.78	1.36:1:2.54
	14	28.37	21.93	49.70	1.29:1:2.27
	20	26.94	23.59	49.47	1.14:1:2.10

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Solvothermal Preparation and Growth Mechanism of CuInS₂ Thin Films of Nanosheet Array

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