Article, Temperature-Dependent Crystalliza[tion, Strain Evolution, and Structural Stability of Chemically Synthesized MoS₂ under Sulfur-Assisted Annealing
Temperature-Dependent Crystalliza[tion, Strain Evolution, and Structural Stability of Chemically Synthesized MoS₂ under Sulfur-Assisted Annealing
DOI:
https://doi.org/10.65273/hhit.jna.2026.2.3.055Keywords:
MoS₂, thermal annealing, crystallization, Raman spectroscopy, X-ray diffraction, FE-SEM, layered transition-metal dichalcogenideAbstract
This study investigates the effect of sulfur-assisted N₂ annealing (300, 500, 700, and 900 °C) on chemically synthesized MoS₂ using Raman spectroscopy, XRD, and FE-SEM. Crystallite size increased from 7.2 nm (300 °C) to 13.5 nm (500 °C) and peaked at 22.1 nm (700 °C), accompanied by a strain reduction from to . At 900°C, crystallite size decreased to 18.4 nm and strain increased to , indicating structural deterioration. FE-SEM revealed stacked, flake-like nanostructures with lateral dimensions of 50–100 nm and aggregate thicknesses of 20–30 nm. Annealing at 700 °C provided the optimal balance between crystallite growth and strain relief. The decline at 900 °C is attributed to lattice distortion and potential sulfur non-stoichiometry, establishing a quantitative baseline for thermal processing of MoS₂
Downloads
References
[1] X. Huang, Z. Zeng, and H. Zhang, (2013). Metal dichalcogenide nanosheets: Preparation, properties and applications, Chem. Soc. Rev., 42(5), 1934–19461945. https://doi.org/10.1039/C2CS35387C
[2] M. Chhowalla, H. S. Shin, G. Eda, L. J. Li, K. P. Loh, and H. Zhang, (2013). The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets, Nat. Chem., 5(4), 263–275. https://doi.org/10.1038/nchem.1589
[3] Q. H. Wang, K. Kalantar-Zadeh, A. Kis, J. N. Coleman, and M. S. Strano, (2012). Electronics and optoelectronics of two-dimensional transition metal dichalcogenides, Nat. Nanotechnol., 7(11), 699–712. https://doi.org/10.1038/nnano.2012.193
[4] S. Manzeli, D. Ovchinnikov, D. Pasquier, O. V. Yazyev, and A. Kis, (2017). 2D transition metal dichalcogenides, Nat. Rev. Mater., 2(8), 17033. https://doi.org/10.1038/natrevmats.2017.33
[5] U. Krishnan, M. Kaur, K. Singh, M. Kumar, A. Kumar, (2019). A synoptic review of MoS2: Synthesis to applications, Superlattices Microstruct., 128, 274–297. https://doi.org/10.1016/j.spmi.2019.02.005
[6] B. Radisavljevic, A. Radenovic, J. Brivio, V. Giacometti, and A. Kis, (2011). Single-layer MoS₂ transistors, Nat. Nanotechnol., 6(3), 147–150. https://doi.org/10.1038/nnano.2010.279
[7] D. Jariwala, V. K. Sangwan, L. J. Lauhon, T. J. Marks, and M. C. Hersam, (2014). Emerging device applications for semiconductor two-dimensional transition metal dichalcogenides, ACS Nano, 8(2), 1102–1120. https://doi.org/10.1021/nn500064s
[8] H. Li, Z. Yin, Q. He, H. Li, X. Huang, G. Lu, D. W. H. Fam, A. Y. Tok, Q. Zhang, H. Zhang, (2012). Fabrication of single- and multilayer MoS2 film-based field-effect transistors for sensing NO at room temperature, Small, 8(1), 63–67. https://doi.org/10.1002/smll.201101016
[9] K. F. Mak, C. Lee, J. Hone, J. Shan, and T. F. Heinz, (2010). Atomically thin MoS₂: A new direct-gap semiconductor, Phys. Rev. Lett., 105(13), 136805. https://doi.org/10.1103/PhysRevLett.105.136805
[10] A. Splendiani, L. Sun, Y. Zhang, T. Li, J. Kim, C. Y. Chim, G. Galli, and F. Wang, (2010). Emerging photoluminescence in monolayer MoS₂, Nano Lett., 10(4), 1271–1275.
https://doi.org/10.1021/nl903868w
[11] J. Shi, D. Ma, G. F. Han, Y. Zhang, Q. Ji, T. Gao, J. Sun, X. Song, C. Li, Y. Zhang, X.-Y. Lang, Y. Zhang, and Z. Liu, (2014). Controllable growth and transfer of monolayer MoS₂ on Au foils and its potential application in hydrogen evolution reaction, ACS Nano, 8(10), 10196–10204. https://doi.org/10.1021/nn503211t
[12] K. Chang and W. Chen, (2011). L-Cysteine-assisted synthesis of layered MoS₂/graphene composites with excellent electrochemical performances for lithium ion batteries, ACS Nano, 5(6), 4720–4728. https://doi.org/10.1021/nn200659w
[13] Ronge, E.; Hildebrandt, S.; Grutza, M.-L.; Klein, H.; Kurz, P.; Jooss, C. (2020) Structure of nanocrystalline, partially disordered MoS₂+δ derived from HRTEM An abundant material for efficient HER catalysis. Catal., 10 (8), 856. https://doi.org/10.3390/catal10080856
[14] H. J. Conley, B. Wang, J. I. Ziegler, R. F. Haglund Jr., S. T. Pantelides, and K. I. Bolotin, (2013). Bandgap engineering of strained monolayer and bilayer MoS₂, Nano Lett., 13(8), 3626–3630.
https://doi.org/10.1021/nl4014748
[15] Mitra, S.; Srivastava, D.; Singha, S.S.; Dutta, S.; Satpati, B.; Karppinen, M.; Ghosh, A.; Singha, A. (2020) Tailoring phonon modes of few-layered MoS₂ by in-plane electric field. npj 2D Mater. Appl., 4, 6. https://doi.org/10.1038/s41699-020-0138-y.
[16] Sam, R.T.; Umakoshi, T.; Verma, P. (2020). Probing stacking configurations in a few layered MoS₂ by low frequency Raman spectroscopy. Sci. Rep., 10, 21227.
https://doi.org/10.1038/s41598-020-78238-w.
[17] H. Li, Q. Zhang, C. C. R. Yap, B. K. Tay, T. H. T. Edwin, A. Olivier, and D. Baillargeat, (2012). From bulk to monolayer MoS₂: Evolution of Raman scattering, Adv. Funct. Mater., 22(7), 1385–1390.
https://doi.org/10.1002/adfm.201102111
[18] C. Lee, H. Yan, L. E. Brus, T. F. Heinz, J. Hone, and S. Ryu, (2010). Anomalous lattice vibrations of single- and few-layer MoS₂, ACS Nano, 4(5), 2695–2700. https://doi.org/10.1021/nn1003937
[19] A. Berkdemir, H. R. Gutierrez, A. R. Botello-Mendez, N. Perea-Lopez, A. L. Elias, C. I. Chia, B. Wang, V. H. Crespi, F. Lopez-Urias, J. C. Charlier, and H. Terrones, (2013). Identification of individual and few layers of WS₂ using Raman spectroscopy, Sci. Rep., 3(1), 1755. https://doi.org/10.1038/srep01755
[20] M. Chhowalla, H. S. Shin, G. Eda, L.-J. Li, K. P. Loh, and H. Zhang, (2013). The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets, Nat. Chem., 5(4), 263–275.
https://doi.org/10.1038/nchem.1589
[21] X. Huang, C. Tan, Z. Yin, and H. Zhang, (2014). 25th anniversary article: Hybrid nanostructures based on two-dimensional nanomaterials, Adv. Mater., 26(14), 2185–2204.
https://doi.org/10.1002/adma.201304964
[22] Y.-C. Lin, W. Zhang, J.-K. Huang, K.-K. Liu, Y.-H. Lee, C.-T. Liang, C.-W. Chu, and L.-J. Li, (2012). Wafer-scale MoS₂ thin layers prepared by MoO₃ sulfurization, Nanoscale, 4(20), 6637–6641.
https://doi.org/10.1039/C2NR31833D
[23] Y. H. Lee, X. Q. Zhang, W. Zhang, M. T. Chang, C.-T. Lin, K.-D. Chang, Y.-C. Yu, J. T.-W. Wang, C.-S. Chang, L.-J. Li, T.-W. Lin, (2012). Synthesis of large-area MoS₂ atomic layers with chemical vapor deposition, Adv. Mater., 24(17), 2320–2325. https://doi.org/10.1002/adma.201104798
[24] K. K. Liu, W. Zhang, Y. H. Lee, Y. C. Lin, M. T. Chang, C. Y. Su, C. S. Chang, H. Li, Y. Shi, H. Zhang, C.-S. Lai, and L. J. Li, (2012). Growth of large-area and highly crystalline MoS₂ thin layers on insulating substrates, Nano Lett., 12(3), 1538–1544. https://doi.org/10.1021/nl2043612
[25] Y. Yu, C. Li, Y. Liu, L. Su, Y. Zhang, and L. Cao, (2013). Controlled scalable synthesis of uniform, high-quality monolayer and few-layer MoS2 films, Sci. Rep., 3(1), 1866.
https://doi.org/10.1038/srep01866
[26] A. M. van der Zande, P. Y. Huang, D. A. Chenet, T. C. Berkelbach, Y. You, G. H. Lee, T. F. Heinz, D. R. Reichman, D. A. Muller, and J. C. Hone, (2013). Grains and grain boundaries in highly crystalline monolayer molybdenum disulfide, Nat. Mater., 12(6), 554–561. https://doi.org/10.1038/nmat3633
[27] S. Najmaei, Z. Liu, W. Zhou, X. Zou, G. Shi, S. Lei, B. I. Yakobson, J. C. Idrobo, P. M. Ajayan, and J. Lou, (2013). Vapour phase growth and grain boundary structure of molybdenum disulfide atomic layers, Nat. Mater., 12(8), 754–759. https://doi.org/10.1038/nmat3673
[28] X. Ling, Y. H. Lee, Y. Lin, W. Fang, L. Yu, M. S. Dresselhaus, and J. Kong, (2014). Role of the seeding promoter in MoS₂ growth by chemical vapor deposition, Nano Lett., 14(2), 464–472.
https://doi.org/10.1021/nl4033704
[29] Y. Zhan, Z. Liu, S. Najmaei, P. M. Ajayan, and J. Lou, (2012). Large-area vapor-phase growth and characterization of MoS₂ atomic layers on a SiO₂ substrate, Small, 8(7), 966–971.
https://doi.org/10.1002/smll.201102654
[30] J. Zheng, H. Zhang, S. Dong, Y. Liu, C. T. Nai, H. S. Shin, H. Y. Jeong, B. Liu, and K. P. Loh, (2014). High yield exfoliation of two-dimensional chalcogenides using sodium naphthalenide, Nat. Commun., 5(1), 2995. https://doi.org/10.1038/ncomms3995
[31] X. Fan, P. Xu, D. Zhou, Y. Sun, Y. C. Li, M. A. T. Nguyen, M. Terrones, and T. E. Mallouk, (2015). Fast and efficient preparation of exfoliated 2H MoS₂ nanosheets by sonication-assisted lithium intercalation and infrared laser-induced 1T to 2H phase reversion, Nano Lett., 15(9), 5956–5960.
https://doi.org/10.1021/acs.nanolett.5b02091
[32] P. Joensen, R. F. Frindt, and S. R. Morrison, (2008). Single-layer MoS₂, Mater. Res. Bull., 21(4), 457–461. https://doi.org/10.1016/0025-5408(86)90011-5
[33] S. S. Chou, B. Kaehr, J. Kim, B. M. Foley, M. De, P. E. Hopkins, J. Huang, C. J. Brinker, and V. P. Dravid, (2013). Chemically exfoliated MoS₂ as near-infrared photothermal agents, Angew. Chem. Int. Ed., 52(15), 4160–4164. https://doi.org/10.1002/anie.201209229
[34] Desai, P.; Todankar, B.; Ranade, A.K.; Kondo, M.; Dewa, T.; Tanemura, M.; Kalita, G., (2021). Synthesis of MoS₂ Layers on GaN Using Ammonium Tetrathiomolybdate for Heterojunction Device Applications. Cryst. Res. Technol., 56(6), 2000198. https://doi.org/10.1002/crat.202000198
[35] J. Lian, H. Liu, S. Han, J. Lian, (2021). MoS₂ nanosheet-polypyrrole composites deposited on reduced graphene oxide for supercapacitor applications. ACS Appl. Nano Mater., 4, 1330–1339.
https://doi.org/10.1021/acsanm.0c02899
[36] H. S. S. R. Matte, A. Gomathi, A. K. Manna, D. J. Late, R. Datta, S. K. Pati, and C. N. R. Rao, (2010). MoS₂ and WS₂ analogues of graphene, Angew. Chem. Int. Ed., 49(24), 4059–4062.
https://doi.org/10.1002/anie.201000009
[37] Timpel, M.; Ligorio, G.; Ghiami, A.; et al., (2021). 2D-MoS₂ goes 3D: transferring optoelectronic properties of 2D MoS₂ to a large-area thin film. npj 2D Mater. Appl., 5, 64.
https://doi.org/10.1038/s41699-021-00244-x
[38] Kwack, Y.-J.; Can, T.T.T.; Choi, W.-S., (2021). Bottom-up water-based solution synthesis for a large MoS₂ atomic layer for thin-film transistor applications. npj 2D Mater. Appl., 5, 84. https://doi.org/10.1038/s41699-021-00264-7
[39] K.-K. Liu, W. Zhang, Y.-H. Lee, Y.-C. Lin, M.-T. Chang, C.-Y. Su, C.-S. Chang, H. Li, Y. Shi, H. Zhang, C.-S. Lai, and L.-J. Li, (2012). Growth of large-area and highly crystalline MoS₂ thin layers on insulating substrates, Nano Lett., 12(3), 1538–1544. https://doi.org/10.1021/nl2043612
[40] B. Chakraborty, A. Bera, D. V. S. Muthu, S. Bhowmick, U. V. Waghmare, and A. K. Sood, (2012). Symmetry-dependent phonon renormalization in monolayer MoS₂ transistor, Phys. Rev. B, 85(16), 161403(R). https://doi.org/10.1103/PhysRevB.85.161403
[41] H. Sahin, S. Tongay, S. Horzum, W. Fan, J. Zhou, J. Li, J. Wu, and F. M. Peeters, (2013). Anomalous Raman spectra and thickness-dependent electronic properties of WSe2, Phys. Rev. B, 87(16), 165409. https://doi.org/10.1103/PhysRevB.87.165409
[42] Y. Zhao, X. Luo, H. Li, J. Zhang, P. T. Araujo, C. K. Gan, J. Wu, H. Zhang, S. Y. Quek, M. S. Dresselhaus, and Q. Xiong, (2013). Interlayer breathing and shear modes in few-layer MoS₂ and WS2, Nano Lett., 13(3), 1007–1015. https://doi.org/10.1021/nl304169w
[43] M. A. Pimenta, E. del Corro, B. R. Carvalho, C. Fantini, and L. M. Malard, (2015). Comparative study of Raman spectroscopy in graphene and MoS2‑type transition metal dichalcogenides, Acc. Chem. Res., 48(1), 41–47. https://doi.org/10.1021/ar500280m
[44] X. Zhang, Q. H. Tan, J. B. Wu, W. Shi, and P. H. Tan, (2016). Review on the Raman spectroscopy of different types of layered materials, Nanoscale, 8(12), 6435–6450. https://doi.org/10.1039/C5NR07205K
[45] S. Baik, Y. Koo, W. Choi (2022), Decreased n-type behavior of monolayer MoS₂ crystals annealed in sulfur atmosphere. Curr. Appl. Phys., 42, 38–42. https://doi.org/10.1016/j.cap.2022.07.011.
[46] J. Hong, Z. Hu, M. Probert, K. Li, D. Lv, X. Yang, L. Gu, N. Mao, Q. Feng, L. Xie, J. Zhang et. al. (2015). Exploring atomic defects in molybdenum disulfide monolayers, Nat. Commun., 6(1), 6293. https://doi.org/10.1038/ncomms7293
[47] W. Zhou, X. Zou, S. Najmaei, Z. Liu, Y. Shi, J. Kong, J. Lou, P. M. Ajayan, B. I. Yakobson, and J. C. Idrobo, (2013). Intrinsic structural defects in monolayer molybdenum disulfide, Nano Lett., 13(6), 2615–2622. https://doi.org/10.1021/nl4007479
[48] S. Kc, R. C. Longo, R. Addou, R. M. Wallace, and K. Cho, (2014). Impact of intrinsic atomic defects on the electronic structure of MoS₂ monolayers, Nanotechnol., 25(37), 375703.
https://doi.org/10.1088/0957-4484/25/37/375703
[49]. Lee, J.; Kim, M.J.; Jeong, B.G.; Kwon, C.; Cha, Y.; Choi, S.H.; Kim, K.K.; Jeong, M.S. (2023), Electrical role of sulfur vacancies in MoS₂: Transient current approach. Appl. Surf. Sci., 613, 155900. https://doi.org/10.1016/j.apsusc.2022.155900.
[50] D. H. Keum, S. Cho, J. H. Kim, D. H. Choe, H. J. Sung, M. Kan, H. Kang, J. Y. Hwang, S. W. Kim, H. Yang, K. J. Chang, Y. H. Lee (2015). Bandgap opening in few-layered monoclinic MoTe2, Nat. Phys., 11(6), 482–486. https://doi.org/10.1038/nphys3314
[51] Y. Koo, W. Choi, (2023). Effects of forming gas annealing on the doping of monolayer MoS₂ crystals. Curr. Appl. Phys., 48, 29–33. https://doi.org/10.1016/j.cap.2023.01.005.
[52] C. Muratore, J. J. Hu, B. Wang, M. A. Haque, J. E. Bultman, M. L. Jespersen, P. J. Shamberger, M. E. McConney, R. D. Naguy, and A. A. Voevodin, (2014). Continuous ultra-thin MoS₂ films grown by low-temperature physical vapor deposition, Appl. Phys. Lett., 104(26), 261604.
https://doi.org/10.1063/1.4885391
[53] Ștefan Ţălu, Vu Van Thu, Nguyen Dac Dien, (2026), A state of the art review on MoS2 preparations and applications, Journal of Nanomaterials and Applications, 2(2), 1-15, https://doi.org/10.65273/hhit.jna.2026.2.2.028
[54] Z. Lin, B. R. Carvalho, E. Kahn, R. Rao, H. Torrones, M. A. Pimenta, and M. Terrones, (2016). Defect engineering of two-dimensional transition metal dichalcogenides, 2D Mater., 3(2), 022002. https://doi.org/10.1088/2053-1583/3/2/022002
[55] H. Nan, Z. Wang, W. Wang, Z. Liang, Y. Lu, Q. Chen, D. He, P. Tan, F. Miao, X. Wang, J. Wang, and Z. Ni, (2014). Strong photoluminescence enhancement of MoS₂ monolayer by defect engineering, ACS Nano, 8(6), 5738–5745. https://doi.org/10.1021/nn500581q
[56] S. J. Yun, S. H. Chae, H. Kim, J. C. Park, J.-H. Park, G. H. Han, J. S. Lee, S. M. Kim, H. M. Oh, J. Seok, M. S. Jeong, K. K. Kim, and Y. H. Lee, (2015). Synthesis of centimeter-scale monolayer tungsten disulfide film on gold foils, ACS Nano, 9(5), 5510–5519. https://doi.org/10.1021/acsnano.5b01529
[57] Y. C. Lin, D. O. Dumcenco, Y. S. Huang, and K. Suenaga, (2014). Atomic mechanism of the semiconductor-to-metal phase transition in single-layer MoS₂, Nat. Nanotechnol., 9(5), 391–396. https://doi.org/10.1038/nnano.2014.64
[58] Ştefan Ţălu, Dung Nguyen Trong, Umut Sarac, Luong Viet Trung, Mai Ho Thi Thanh, Huong Vuong Thi, (2024), Impact of MoS2 Layer Thickness and Donor Concentration on Saturation Current in 4-Layer MOSFET: A Comsol Simulation, Journal of Science and Transport Technology, 4(4), 19-29, https://doi.org/10.58845/jstt.utt.2024.en.4.4.19-29
Downloads
Published
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request
Issue
Section
License
Copyright (c) 2026 Dung Nguyen Trong, Dien Nguyen Dac, Umut Saraç (Author)
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.
1. Grant of License
The Author(s) hereby grant to the Publisher a non-exclusive, perpetual, worldwide, royalty-free, and irrevocable license to publish, reproduce, distribute, and display the Work in all forms and media, whether now known or hereafter developed. This includes but is not limited to print, online, and digital formats. The Publisher may also license the Work to third parties for inclusion in databases, repositories, and other platforms.
2. Author's Warranties
-The Author(s) warrant and represent that:
-The Work is an original creation of the Author(s).
-The Author(s) have the full power and authority to enter into this Agreement and to grant the rights granted herein.
-The Work has not been previously published or licensed for publication in any other journal or book.
-The Work does not infringe upon any copyright, trademark, privacy right, or other proprietary right of any third party.
-All necessary permissions for the use of third-party materials (e.g., figures, tables) have been obtained by the Author(s) and are properly credited in the Work
3. Author's Rights
-The Author(s) retain the following rights:
-The right to use the Work for their own personal, academic, and research purposes, including posting it on their personal website or institutional repository, provided that the published version is not used and the original publication is acknowledged.
-The right to include the Work, in part or in full, in future works of their own (e.g., books, dissertations), provided that proper credit is given to the original publication in this journal.
Journal of Nanomaterials and Applications (JNA)
Add: 14-15A, 7th floor, Charmvit Tower building, 117 Tran Duy Hung, Trung Hoa, Hanoi, 100000, Vietnam
Phone: 084+0904526939 Email: jna.com.vn@gmail.com / jna@jna.com.vn Website: jna.com.vn
