J. Semicond. > Volume 36 > Issue 3 > Article Number: 033001

Phase transformation from cubic ZnS to hexagonal ZnO by thermal annealing

K. Mahmood 1, , M. Asghar 2, , N. Amin 1, and Adnan Ali 1,

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Abstract: We have investigated the mechanism of phase transformation from ZnS to hexagonal ZnO by high-temperature thermal annealing. The ZnS thin films were grown on Si (001) substrate by thermal evaporation system using ZnS powder as source material. The grown films were annealed at different temperatures and characterized by X-ray diffraction (XRD), photoluminescence (PL), four-point probe, scanning electron microscope (SEM) and energy dispersive X-ray diffraction (EDX). The results demonstrated that as-deposited ZnS film has mixed phases but high-temperature annealing leads to transition from ZnS to ZnO. The observed result can be explained as a two-step process: (1) high-energy O atoms replaced S atoms in lattice during annealing process, and (2) S atoms diffused into substrate and/or diffused out of the sample. The dissociation energy of ZnS calculated from the Arrhenius plot of 1000/T versus log (resistivity) was found to be 3.1 eV. PL spectra of as-grown sample exhibits a characteristic green emission at 2.4 eV of ZnS but annealed samples consist of band-to-band and defect emission of ZnO at 3.29 eV and 2.5 eV respectively. SEM and EDX measurements were additionally performed to strengthen the argument.

Key words: ZnSphase transformationEDXXRDPL

Abstract: We have investigated the mechanism of phase transformation from ZnS to hexagonal ZnO by high-temperature thermal annealing. The ZnS thin films were grown on Si (001) substrate by thermal evaporation system using ZnS powder as source material. The grown films were annealed at different temperatures and characterized by X-ray diffraction (XRD), photoluminescence (PL), four-point probe, scanning electron microscope (SEM) and energy dispersive X-ray diffraction (EDX). The results demonstrated that as-deposited ZnS film has mixed phases but high-temperature annealing leads to transition from ZnS to ZnO. The observed result can be explained as a two-step process: (1) high-energy O atoms replaced S atoms in lattice during annealing process, and (2) S atoms diffused into substrate and/or diffused out of the sample. The dissociation energy of ZnS calculated from the Arrhenius plot of 1000/T versus log (resistivity) was found to be 3.1 eV. PL spectra of as-grown sample exhibits a characteristic green emission at 2.4 eV of ZnS but annealed samples consist of band-to-band and defect emission of ZnO at 3.29 eV and 2.5 eV respectively. SEM and EDX measurements were additionally performed to strengthen the argument.

Key words: ZnSphase transformationEDXXRDPL



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[2]

Wang K, Chen J J, Zeng Z M. Synthesis and photovoltaic effect of vertically aligned ZnO/ZnS core/shell nanowire arrays[J]. Appl Phys Lett, 2010, 96: 123105.

[3]

Jin C, Kim H, Kim H W. Enhancement in the photoluminescence of ZnS nanowires by TiO2 coating and thermal annealing[J]. J Lumin, 2010, 130: 516.

[4]

Lin P C, Hua C C, Lee T C. Low-temperature phase transition of ZnS: the critical role of ZnO[J]. J Solid State Chem, 2012, 194: 282.

[5]

Kryshtab T, Khomchenko V S, Andraca-Adame J A. Luminescence and structure of ZnO—ZnS thin films prepared by oxidation of ZnS films in air and water vapor[J]. J Lumin, 2009, 129: 1677.

[6]

Sunghoon P, Changhyun J, Hyunsu K. Enhanced violet emission from ZnS nanowires annealed in an oxygen atmosphere[J]. J Lumin, 2012, 132: 231.

[7]

Meng C, Lei Z B, Liang L. Effects of zinc salts on the structural and optical properties of acidic chemical bath deposited ZnS thin films[J]. J Mater Research Bulletin, 2013, 48: 357.

[8]

Asghar M, Mahmood K, Ferguson I. Investigation of VO—Zn i native donor complex in MBE grown bulk ZnO[J]. Semicond Sci Technol, 2013, 20: 105019.

[9]

Zack L N, Ziurys L M. The pure rotational spectrum of ZnS (X1Σ +)[J]. J Molecular Spect, 2009, 257: 213.

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Nanda J, Sapra S, Sarma D D. size-selected zinc sulfide nanocrystallites: synthesis, structure, and optical studies[J]. Chem Mater, 2002, 12: 1018.

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Wang C F, Hu B, Li W B. Luminescence properties of ZnS/porous Si composites[J]. Optik, 2014, 125: 554.

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Zhao Y, Zhou M, Lv Z. Effect of K—N on the structural and optical properties of K—N Co-doped ZnO film[J]. Mater Sci Semi Process, 2011, 14: 257.

[13]

Asghar M, Khalid M, Adnan A. Origin of ultraviolet luminescence from bulk ZnO thin films grown by molecular beam epitaxy[J]. Adv Eng Forum, 2011, 1: 135.

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K. Mahmood, M. Asghar, N. Amin, A Ali. Phase transformation from cubic ZnS to hexagonal ZnO by thermal annealing[J]. J. Semicond., 2015, 36(3): 033001. doi: 10.1088/1674-4926/36/3/033001.

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Manuscript received: 11 September 2014 Manuscript revised: Online: Published: 01 March 2015

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