Linear and nonlinear optical response of sulfur-deficient nanocrystallite WS2 thin films

  • Gobinda Pradhan
  • Ashwini Kumar SharmaEmail author
Electronic materials


Multilayered-to-bulk-like films were deposited by pulsed laser deposition at various argon gas deposition pressure where a significant amount of sulfur deficiency was observed. All films showed high atomic disorder and corresponding lattice distortion attributed to the large-scale sulfur deficiency. Instead of continuous film, huge sulfur deficiency created a mixed state of metallic tungsten and WS2 nanocrystals of sizes 4–8 nm throughout the films. The as-deposited WS2 films showed a dramatic shift in linear optical response, with the behavior resembling that of quantum dots. A significantly large reverse saturation absorption and positive nonlinear refraction response was observed in all the films, as measured by the open- and closed-aperture Z-scan experiment under He–Ne laser at 632.8 nm. In addition, third-order nonlinear optical susceptibility of the thin films was found to be of the order of 10−2 esu as measured from Z-scan experiment. The anomalously high nonlinear optical response of the film was attributed to the continuous-wave laser-induced thermal nonlinearity dominance over optical nonlinearity. Optical limiting was also observed in the films where optical limiting thresholds were found to increase with an increase in nonlinear absorption coefficient.



The authors acknowledge CIF, IIT Guwahati for micro-Raman, FETEM, AFM, FESEM and spectroscopic ellipsometer facilities. The authors also acknowledge department of Physics, IIT Guwahati, for XRD and UV–Vis facilities.

Compliance with ethical standards

Conflict of interest

The author(s) declares no competing interests.


  1. 1.
    Gan X, Shiue R-J, Gao Y, Meric I, Heinz TF, Shepard K, Hone J, Assefa S, Englund D (2013) Chip-integrated ultrafast graphene photodetector with high responsivity. Nat Photonics 7(11):883–887CrossRefGoogle Scholar
  2. 2.
    Shelke NT, Karche B (2017) Ultraviolet photosensor based on few layered reduced graphene oxide nanosheets. Appl Surf Sci 418:374–379CrossRefGoogle Scholar
  3. 3.
    Mas-Balleste R, Gomez-Navarro C, Gomez-Herrero J, Zamora F (2011) 2D materials: to graphene and beyond. Nanoscale 3(1):20–30CrossRefGoogle Scholar
  4. 4.
    Butler SZ, Hollen SM, Cao L, Cui Y, Gupta JA, Gutiérrez HR, Heinz TF, Hong SS, Huang J, Ismach AF (2013) Progress, challenges, and opportunities in two-dimensional materials beyond graphene. ACS Nano 7(4):2898–2926CrossRefGoogle Scholar
  5. 5.
    Beshkova M, Hultman L, Yakimova R (2016) Device applications of epitaxial graphene on silicon carbide. Vacuum 128:186–197CrossRefGoogle Scholar
  6. 6.
    Wang G, Dang S, Zhang P, Xiao S, Wang C, Zhong M (2017) Hybrid density functional study on the photocatalytic properties of AlN/MoSe2, AlN/WS2, and AlN/WSe2 heterostructures. J Phys D 51(2):025109CrossRefGoogle Scholar
  7. 7.
    Liu X, Hu J, Yue C, Della Fera N, Ling Y, Mao Z, Wei J (2014) High performance field-effect transistor based on multilayer tungsten disulfide. ACS Nano 8(10):10396–10402CrossRefGoogle Scholar
  8. 8.
    Elías AL, Perea-Lopez N, Castro-Beltran A, Berkdemir A, Lv R, Feng S, Long AD, Hayashi T, Kim YA, Endo M (2013) Controlled synthesis and transfer of large-area WS2 sheets: from single layer to few layers. ACS Nano 7(6):5235–5242CrossRefGoogle Scholar
  9. 9.
    Ovchinnikov D, Allain A, Huang Y-S, Dumcenco D, Kis A (2014) Electrical transport properties of single-layer WS2. ACS Nano 8(8):8174–8181CrossRefGoogle Scholar
  10. 10.
    Iqbal MW, Iqbal MZ, Khan MF, Shehzad MA, Seo Y, Park JH, Hwang C, Eom J (2015) High-mobility and air-stable single-layer WS2 field-effect transistors sandwiched between chemical vapor deposition-grown hexagonal BN films. Sci Rep 5:10699CrossRefGoogle Scholar
  11. 11.
    Guo H, Lan C, Zhou Z, Sun P, Wei D, Li C (2017) Transparent, flexible, and stretchable WS2 based humidity sensors for electronic skin. Nanoscale 9(19):6246–6253CrossRefGoogle Scholar
  12. 12.
    Lan C, Zhou Z, Zhou Z, Li C, Shu L, Shen L, Li D, Dong R, Yip S, Ho JC (2018) Wafer-scale synthesis of monolayer WS2 for high-performance flexible photodetectors by enhanced chemical vapor deposition. Nano Res 11(6):3371–3384CrossRefGoogle Scholar
  13. 13.
    Ratha S, Rout CS (2013) Supercapacitor electrodes based on layered tungsten disulfide-reduced graphene oxide hybrids synthesized by a facile hydrothermal method. ACS Appl Mater Interfaces 5(21):11427–11433CrossRefGoogle Scholar
  14. 14.
    Godin K, Kang K, Fu S, Yang E-H (2016) Increased monolayer domain size and patterned growth of tungsten disulfide through controlling surface energy of substrates. J Phys D 49(32):325304CrossRefGoogle Scholar
  15. 15.
    Walck S, Zabinski J, Donley M, Bultman J (1993) Evolution of surface topography in pulsed-laser-deposited thin films of MoS2. Surf Coat Technol 62(1–3):412–416CrossRefGoogle Scholar
  16. 16.
    Bruncko J, Šutta P, Netrvalová M, Michalka M, Vincze A, Kovac J (2017) Comparative study of ZnO thin film prepared by pulsed laser deposition—comparison of influence of different ablative lasers. Vacuum 138:184–190CrossRefGoogle Scholar
  17. 17.
    Fominski VY, Grigoriev S, Romanov R, Volosova M, Demin M (2015) Chemical composition, structure and light reflectance of W–Se and W–Se–C films prepared by pulsed laser deposition in rare and reactive buffer gases. Vacuum 119:19–29CrossRefGoogle Scholar
  18. 18.
    Zhu B, Sun X, Zhao X, Su F, Li G, Wu X, Wu J, Wu R, Liu J (2008) The effects of substrate temperature on the structure and properties of ZnO films prepared by pulsed laser deposition. Vacuum 82(5):495–500CrossRefGoogle Scholar
  19. 19.
    Debelo N, Dejene F, Roro K, Pricilla M, Oliphant C (2016) The effect of argon gas pressure on structural, morphological and photoluminescence properties of pulsed laser deposited KY3F10:Ho3+ thin films. Appl Phys A 122(6):619CrossRefGoogle Scholar
  20. 20.
    Dey PP, Khare A (2017) Stoichiometry-dependent linear and nonlinear optical properties of PLD SiOx thin films. J Alloys Compd 706:370–376CrossRefGoogle Scholar
  21. 21.
    Yao J, Zheng Z, Shao J, Yang G (2015) Stable, highly-responsive and broadband photodetection based on large-area multilayered WS2 films grown by pulsed-laser deposition. Nanoscale 7(36):14974–14981CrossRefGoogle Scholar
  22. 22.
    Loh TA, Chua DH, Wee AT (2015) One-step synthesis of few-layer WS2 by pulsed laser deposition. Sci Rep 5:18116CrossRefGoogle Scholar
  23. 23.
    Loh TA, Chua DH (2015) Origin of hybrid 1T- and 2H-WS2 ultrathin layers by pulsed laser deposition. J Phys Chem C 119(49):27496–27504CrossRefGoogle Scholar
  24. 24.
    Yang Z, Hao J (2016) Progress in pulsed laser deposited two-dimensional layered materials for device applications. J Mater Chem C 4(38):8859–8878CrossRefGoogle Scholar
  25. 25.
    Schenato M, Ricardo CLA, Scardi P, Edla R, Miotello A, Orlandi M, Morrish R (2016) Effect of annealing and nanostructuring on pulsed laser deposited WS2 for HER catalysis. Appl Catal A 510:156–160CrossRefGoogle Scholar
  26. 26.
    Torres-Torres C, Perea-López N, Elías AL, Gutiérrez HR, Cullen DA, Berkdemir A, López-Urías F, Terrones H, Terrones M (2016) Third order nonlinear optical response exhibited by mono-and few-layers of WS2. 2D Mater 3(2):021005CrossRefGoogle Scholar
  27. 27.
    Zheng X, Zhang Y, Chen R, Xu Z, Jiang T (2015) Z-scan measurement of the nonlinear refractive index of monolayer WS2. Opt Exp 23(12):15616–15623CrossRefGoogle Scholar
  28. 28.
    Dey PP, Khare A (2017) Nonlinear optical and optical limiting response of PLD nc-Si thin films. J Mater Chem C 5(46):12211–12220CrossRefGoogle Scholar
  29. 29.
    Liang G, Tao L, Tsang YH, Zeng L, Liu X, Li J, Qu J, Wen Q (2019) Optical limiting properties of a few-layer MoS2/PMMA composite under excitation of ultrafast laser pulses. J Mater Chem C 7(3):495–502CrossRefGoogle Scholar
  30. 30.
    Chen T-H, Lin C-Y, Lin Y-H, Chi Y-C, Cheng C-H, Luo Z, Lin G-R (2016) MoS2 nano-flake doped polyvinyl alcohol enabling polarized soliton mode-locking of a fiber laser. J Mater Chem C 4(40):9454–9459CrossRefGoogle Scholar
  31. 31.
    Friberg S, Smith P (1987) Nonlinear optical glasses for ultrafast optical switches. IEEE J Quantum Electron 23(12):2089–2094CrossRefGoogle Scholar
  32. 32.
    Weber M, Milam D, Smith W (1978) Nonlinear refractive index of glasses and crystals. Opt Eng 17(5):175463CrossRefGoogle Scholar
  33. 33.
    Owyoung A (1973) Ellipse rotation studies in laser host materials. IEEE J Quantum Electron 9(11):1064–1069CrossRefGoogle Scholar
  34. 34.
    Sheik-Bahae M, Said AA, Van Stryland EW (1989) High-sensitivity, single-beam n2 measurements. Opt Lett 14(17):955–957CrossRefGoogle Scholar
  35. 35.
    Berkdemir A, Gutiérrez HR, Botello-Méndez AR, Perea-López N, Elías AL, Chia C-I, Wang B, Crespi VH, López-Urías F, Charlier J-C (2013) Identification of individual and few layers of WS2 using Raman spectroscopy. Sci Rep 3:1755CrossRefGoogle Scholar
  36. 36.
    Zhu Q, Chu X, Zhang Z, Dai W-L, Fan K (2013) A novel green process for the synthesis of glutaraldehyde by WS2@ HMS material with aqueous H2O2. RSC Adv 3(6):1744–1747CrossRefGoogle Scholar
  37. 37.
    Acsente T, Negrea RF, Nistor LC, Logofatu C, Matei E, Birjega R, Grisolia C, Dinescu G (2015) Synthesis of flower-like tungsten nanoparticles by magnetron sputtering combined with gas aggregation. Eur Phys J D 69(6):161CrossRefGoogle Scholar
  38. 38.
    Lu M, Chien C (1990) Structural and magnetic properties of Fe–W alloys. J Appl Phys 67(9):5787–5789CrossRefGoogle Scholar
  39. 39.
    Zheng D, Wu Y-p, Li Z-y, Cai Z-b (2017) Tribological properties of WS2/graphene nanocomposites as lubricating oil additives. RSC Adv 7(23):14060–14068CrossRefGoogle Scholar
  40. 40.
    Zabinski J, Donley M, Prasad S, McDevitt N (1994) Synthesis and characterization of tungsten disulphide films grown by pulsed-laser deposition. J Mater Sci 29(18):4834–4839. CrossRefGoogle Scholar
  41. 41.
    Alfihed S, Hossain M, Alharbi A, Alyamani A, Alharbi FH (2013) PLD grown polycrystalline tungsten disulphide (WS2) films. J Mater 2013Google Scholar
  42. 42.
    Pradhan G, Sharma AK (2019) Temperature controlled 1T/2H phase ratio modulation in mono-and a few layered MoS2 films. Appl Surf Sci 479:1236–1245CrossRefGoogle Scholar
  43. 43.
    Liu Y, Xu G, Song C, Weng W, Du P, Han G (2007) Modification on Forouhi and Bloomer model for the optical properties of amorphous silicon thin films. Thin Solid Films 515(7–8):3910–3913CrossRefGoogle Scholar
  44. 44.
    McGahan WA, Makovicka T, Hale J, Woollam JA (1994) Modified Forouhi and Bloomer dispersion model for the optical constants of amorphous hydrogenated carbon thin films. Thin Solid Films 253(1–2):57–61CrossRefGoogle Scholar
  45. 45.
    Sundari ST (2005) Forouhi–Bloomer analysis to study amorphization in Si. J Non-Cryst Solids 351(52–54):3866–3869CrossRefGoogle Scholar
  46. 46.
    Bayat A, Saievar-Iranizad E (2017) Synthesis of blue photoluminescent WS2 quantum dots via ultrasonic cavitation. J Lumin 185:236–240CrossRefGoogle Scholar
  47. 47.
    Yan Y, Zhang C, Gu W, Ding C, Li X, Xian Y (2016) Facile synthesis of water-soluble WS2 quantum dots for turn-on fluorescent measurement of lipoic acid. J Phys Chem C 120(22):12170–12177CrossRefGoogle Scholar
  48. 48.
    Ahn C, Lee J, Kim HU, Bark H, Jeon M, Ryu GH, Lee Z, Yeom GY, Kim K, Jung J (2015) Low-temperature synthesis of large-scale molybdenum disulfide thin films directly on a plastic substrate using plasma-enhanced chemical vapor deposition. Adv Mater 27(35):5223–5229CrossRefGoogle Scholar
  49. 49.
    Kumar I, Khare A (2016) Optical nonlinearity in nanostructured carbon thin films fabricated by pulsed laser deposition technique. Thin Solid Films 611:56–61CrossRefGoogle Scholar
  50. 50.
    Bharti GP, Khare A (2016) Structural and linear and nonlinear optical properties of Zn1−xAlxO (0 ≤ x ≤ 0.10) thin films fabricated via pulsed laser deposition technique. Opt Mater Exp 6(6):2063–2080CrossRefGoogle Scholar
  51. 51.
    Kesarwani R, Khare A (2018) Surface plasmon resonance and nonlinear optical behavior of pulsed laser-deposited semitransparent nanostructured copper thin films. Appl Phys B 124(6):116CrossRefGoogle Scholar
  52. 52.
    Dong N, Li Y, Zhang S, McEvoy N, Zhang X, Cui Y, Zhang L, Duesberg GS, Wang J (2016) Dispersion of nonlinear refractive index in layered WS2 and WSe2 semiconductor films induced by two-photon absorption. Opt Lett 41(17):3936–3939CrossRefGoogle Scholar
  53. 53.
    Bayesteh S, Mortazavi SZ, Reyhani A (2018) Investigation on nonlinear optical properties of MoS2 nanoflakes grown on silicon and quartz substrates. J Phys D 51(19):195302CrossRefGoogle Scholar
  54. 54.
    Dey PP, Khare A (2016) Effect of substrate temperature on structural and linear and nonlinear optical properties of nanostructured PLD a-SiC thin films. Mater Res Bull 84:105–117CrossRefGoogle Scholar
  55. 55.
    Rumaner L, Tazawa T, Ohuchi F (1994) Compositional change of (0001) WS2 surfaces induced by ion beam bombardment with energies between 100 and 1500 eV. J Vac Sci Technol 12(4):2451–2456CrossRefGoogle Scholar
  56. 56.
    Li D-H, Zheng H, Wang Z-Y, Zhang R-J, Zhang H, Zheng Y-X, Wang S-Y, Zhang DW, Chen L-Y (2017) Dielectric functions and critical points of crystalline WS2 ultrathin films with tunable thickness. Phys Chem Chem Phys 19(19):12022–12031CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of PhysicsIndian Institute of Technology GuwahatiGuwahatiIndia

Personalised recommendations