, Volume 14, Issue 1, pp 205–218 | Cite as

Investigation of Broadband Surface Plasmon Resonance of Dewetted Au Structures on TiO2 by Aperture-Probe SNOM and FDTD Simulations

  • J. Abed
  • F. Alexander
  • I. Taha
  • N. Rajput
  • C. Aubry
  • M. JouiadEmail author


The surface plasmon resonance of dewetted Au structures on TiO2 substrate using physical vapor deposition and post-annealing is investigated. In this work, we employ an aperture-probe scanning near-field optical microscope (SNOM) to study the plasmonic properties of dewetted Au structures and the influence of the size, shape, and interdistance of the dewetted structures on their plasmonic behavior. This investigation is corroborated by numerical calculations performed using finite-difference time-domain (FDTD) and atomic force microscopy (AFM) to provide a realistic and direct comparison with SNOM experiments. The near-field images obtained by both experiments and simulations reveal surface plasmon resonance around Au structures which are correlated to the broadband activity in the visible light region observed by UV-Vis spectrophotometry and photoluminescence. In addition, near-field enhancement is associated with the external quantum efficiency (EQE), which shows a multi-peak response after 570 nm due higher-order modes of plasmon resonance. This broadband improvement in the visible region obtained by controlled dewetting has potential use in large-scale solar energy applications.

Graphical Abstract


Plasmonics Au structures SNOM FDTD simulations 



This work was carried out using the state-of-the-art clean room and electron microscopy facilities of Masdar Institute of Science and Technology. The authors would like to thank Prof. Kim Sang-Gook (MIT-USA) for the fruitful discussions and Hitesh Mamgain, WITec™ for the valuable hints on SNOM experiments.


  1. 1.
    Alami AH, Alketbi A, Abed J, Almheiri M (2016) Assessment of Al-Cu-Fe compound for enhanced solar absorption. Int J Energy Res 40:514–521. Google Scholar
  2. 2.
    Alami AH, Abed J, Almheiri M, Alketbi A, Aokal C (2016) Fe-Cu metastable material as a mesoporous layer for dye-sensitized solar cells. Energy Sci Eng 4:166–179. Google Scholar
  3. 3.
    Nishikiori H, Qian W, El-Sayed MA et al (2007) Change in titania structure from amorphousness to crystalline increasing photoinduced electron-transfer rate in dye-titania system. J Phys Chem C 111:9008–9011. Google Scholar
  4. 4.
    Benko G, Skarman B, Wallenberg R et al (2003) Particle size and crystallinity dependent electron injection in fluorescein 27-sensitized TiO2 films. J Phys Chem B 107:1370–1375. Google Scholar
  5. 5.
    Choi W, Termin A, Hoffmann MR (1994) The role of metal ion dopants in quantum-sized TiO2: correlation between photoreactivity and charge carrier recombination dynamics. J Phys Chem 98:13669–13679. Google Scholar
  6. 6.
    Umebayashi T, Yamaki T, Itoh H, Asai K (2002) Band gap narrowing of titanium dioxide by sulfur doping. Appl Phys Lett 81:454–456. Google Scholar
  7. 7.
    Dvoranová D, Brezová V, Mazúr M, Malati MA (2002) Investigations of metal-doped titanium dioxide photocatalysts. Appl Catal B Environ 37:91–105. Google Scholar
  8. 8.
    Vogel R, Hoyer P, Weller H (1994) Quantum-sized PbS, CdS, Ag2S, Sb2S3, and Bi2S3 particles as sensitizers for various nanoporous wide-bandgap semiconductors. J Phys Chem 98:3183–3188. Google Scholar
  9. 9.
    GURUNATHAN K (1997) Photocatalytic hydrogen production by dye-sensitized Pt/SnO2 AND Pt/SnO2/RuO2 in aqueous methyl viologen solution. Int J Hydrog Energy 22:57–62. Google Scholar
  10. 10.
    Gopidas KR, Bohorquez M, Kamat PV (1990) Photophysical and photochemical aspects of coupled semiconductors. Charge-transfer processes in colloidal CdS-TiO, and CdS-AgI systems. J Phys Chem 94:6435–6440. Google Scholar
  11. 11.
    SEAN T. SIVAPALAN (2013) Structural and plasmonic properties of gold nanocrystals. University of Illinois at Urbana-ChampaignGoogle Scholar
  12. 12.
    Zhang J, Zhang L (2012) Nanostructures for surface plasmons. Adv Opt Photonics 4:157. Google Scholar
  13. 13.
    Warren SC, Thimsen E (2012) Plasmonic solar water splitting. Energy Environ Sci 5:5133–5146. Google Scholar
  14. 14.
    Muduli S, Game O, Dhas V, Vijayamohanan K, Bogle KA, Valanoor N, Ogale SB (2012) TiO2-Au plasmonic nanocomposite for enhanced dye-sensitized solar cell (DSSC) performance. Sol Energy 86:1428–1434. Google Scholar
  15. 15.
    Jang YH, Jang YJ, Kochuveedu ST, Byun M, Lin Z, Kim DH (2014) Plasmonic dye-sensitized solar cells incorporated with Au–TiO 2 nanostructures with tailored configurations. Nanoscale 6:1823–1832. Google Scholar
  16. 16.
    Lim SP, Pandikumar A, Huang NM, Lim HN (2015) Facile synthesis of Au@TiO 2 nanocomposite and its application as a photoanode in dye-sensitized solar cells. RSC Adv 5:44398–44407. Google Scholar
  17. 17.
    Chou JB, Wang Y, Fenning DP, et al (2016) Surface plasmon assisted hot electron collection in wafer-scale metallic- semiconductor photonic crystals. 24:3510–3514.
  18. 18.
    Zhang X, Chen YL, Liu R-S, Tsai DP (2013) Plasmonic photocatalysis. Rep Prog Phys 76:046401. Google Scholar
  19. 19.
    Clavero C (2014) Plasmon-induced hot-electron generation at nanoparticle/metal-oxide interfaces for photovoltaic and photocatalytic devices. Nat Photonics 8:95–103. Google Scholar
  20. 20.
    Fang Y, Jiao Y, Xiong K, Ogier R, Yang ZJ, Gao S, Dahlin AB, Käll M (2015) Plasmon enhanced internal photoemission in antenna-spacer-mirror based Au/TiO<inf>2</inf> nanostructures. Nano Lett 15:4059–4065. Google Scholar
  21. 21.
    Rajput NS, Shao-Horn Y, Li X-H, Kim SG, Jouiad M (2017) Investigation of plasmon resonance in metal/dielectric nanocavities for high-efficiency photocatalytic device. Phys Chem Chem Phys 19:16989–16999. Google Scholar
  22. 22.
    Wu N (2018) Plasmonic metal-semiconductor photocatalysts and photoelectrochemical cells: a review.
  23. 23.
    Tian Y, Tatsuma T (2005) Mechanisms and applications of plasmon-induced charge separation at TiO2 films loaded with gold nanoparticles. J Am Chem Soc 127:7632–7637. Google Scholar
  24. 24.
    Silva CG, Juárez R, Marino T et al (2011) Influence of excitation wavelength (UV or visible light) on the photocatalytic activity of titania containing gold nanoparticles for the generation of hydrogen or oxygen from water. J Am Chem Soc 133:595–602. Google Scholar
  25. 25.
    Arabatzis IM, Stergiopoulos T, Bernard MC, Labou D, Neophytides SG, Falaras P (2003) Silver-modified titanium dioxide thin films for efficient photodegradation of methyl orange. Appl Catal B Environ 42:187–201. Google Scholar
  26. 26.
    Cushing SK, Li J, Meng F et al (2012) Photocatalytic activity enhanced by plasmonic resonant energy transfer from metal to semiconductor. J Am Chem Soc 4.
  27. 27.
    Brongersma ML, Halas NJ, Nordlander P (2015) Plasmon-induced hot carrier science and technology. Nat Nanotechnol 10:25–34. Google Scholar
  28. 28.
    Tan F, Li T, Wang N, Lai SK, Tsoi CC, Yu W, Zhang X (2016) Rough gold films as broadband absorbers for plasmonic enhancement of TiO2 photocurrent over 400–800 nm. Sci Rep 6:33049. Google Scholar
  29. 29.
    Ng C, Cadusch JJ, Dligatch S, Roberts A, Davis TJ, Mulvaney P, Gómez DE (2016) Hot carrier extraction with plasmonic broadband absorbers. ACS Nano 10:4704–4711. Google Scholar
  30. 30.
    Sousa-Castillo A, Comesana-Hermo M, Rodriguez-Gonzalez B et al (2016) Boosting hot electron-driven photocatalysis through anisotropic plasmonic nanoparticles with hot spots in Au-TiO2 nanoarchitectures. J Phys Chem C 120:11690–11699. Google Scholar
  31. 31.
    Hou W, Hung WH, Pavaskar P, Goeppert A, Aykol M, Cronin SB (2011) Photocatalytic conversion of CO2 to hydrocarbon fuels via plasmon-enhanced absorption and metallic interband transitions. ACS Catal 1:929–936. Google Scholar
  32. 32.
    Guo L, Liang K, Marcus K, Li Z, Zhou L, Mani PD, Chen H, Shen C, Dong Y, Zhai L, Coffey KR, Orlovskaya N, Sohn YH, Yang Y (2016) Enhanced photoelectrocatalytic reduction of oxygen using Au@TiO 2 plasmonic film. ACS Appl Mater Interfaces 8:34970–34977. Google Scholar
  33. 33.
    Ghasemi S, Hashemian SJ, Alamolhoda AA, Gocheva I, Rahman Setayesh S (2017) Plasmon enhanced photocatalytic activity of Au@TiO2-graphene nanocomposite under visible light for degradation of pollutants. Mater Res Bull 87:40–47. Google Scholar
  34. 34.
    Yan M, Dai J, Qiu M (2014) Lithography-free broadband visible light absorber based on a mono-layer of gold nanoparticles. J Opt (United Kingdom) 16:025002. Google Scholar
  35. 35.
    Altomare M, Nguyen NT, Schmuki P (2016) Templated dewetting: designing entirely self-organized platforms for photocatalysis. Chem Sci 7:6865–6886. Google Scholar
  36. 36.
    Nguyen NT, Altomare M, Yoo J, Schmuki P (2015) Efficient photocatalytic H<inf>2</inf> evolution: controlled dewetting-dealloying to fabricate site-selective high-activity nanoporous Au particles on highly ordered TiO<inf>2</inf> nanotube arrays. Adv Mater 27:3208–3215. Google Scholar
  37. 37.
    Marchuk K, Willets KA (2014) Localized surface plasmons and hot electrons. Chem Phys 445:95–104. Google Scholar
  38. 38.
    Li B, Huang L, Zhou M, Ren NF, Wu B (2014) Surface morphology and photoelectric properties of fluorine-doped tin oxide thin films irradiated with 532nm nanosecond laser. Ceram Int 40:1627–1633. Google Scholar
  39. 39.
    Andrae P, Song M, Haggui M, et al (2015) Mapping near-field plasmonic interactions of silver particles with scanning near-field optical microscopy measurements. 9547:95470E.
  40. 40.
    Neuman T, Alonso-González P, Garcia-Etxarri A, Schnell M, Hillenbrand R, Aizpurua J (2015) Mapping the near fields of plasmonic nanoantennas by scattering-type scanning near-field optical microscopy. Laser Photonics Rev 9:637–649. Google Scholar
  41. 41.
    Colliex C, Kociak M, Stéphan O (2016) Electron energy loss spectroscopy imaging of surface plasmons at the nanometer scale. Ultramicroscopy 162:A1–A24. Google Scholar
  42. 42.
    Denkova D, Verellen N, Silhanek A V., et al (2014) Near-field aperture-probe as a magnetic dipole source and optical magnetic field detectorGoogle Scholar
  43. 43.
    Denkova D (2016) Optical characterization of plasmonic nanostructures: near-field imaging of the magnetic field of light 3168:35–53.
  44. 44.
    Denkova D, Verellen N, Silhanek AV, Valev VK, Dorpe PV, Moshchalkov VV (2013) Mapping magnetic near-field distributions of plasmonic nanoantennas. ACS Nano 7:3168–3176. Google Scholar
  45. 45.
    Mizobata H, Hasegawa S, Imura K (2017) Development of aperture-type near-field reflection spectroscopy and its application to single silver nanoplates. J Phys Chem C 121:11733–11739. Google Scholar
  46. 46.
    Lin H-Y, Huang C-H, Chang C-H et al (2010) Direct near-field optical imaging of plasmonic resonances in metal nanoparticle pairs. Opt Express 18:165–172. Google Scholar
  47. 47.
    Fang Z, Zhu X (2013) Plasmonics in nanostructures. Adv Mater 25:3840–3856. Google Scholar
  48. 48.
    Adam PM, Benrezzak S, Bijeon JL, Royer P (2000) Localized surface plasmons on nanometric gold particles observed with an apertureless scanning near-field optical microscope. J Appl Phys 88:6919–6921. Google Scholar
  49. 49.
    Imura K, Nagahara T, Okamoto H (2005) Near-field optical imaging of plasmon modes in gold nanorods. J Chem Phys 122:154701. Google Scholar
  50. 50.
    Abed J, AlMheiri M, Alexander F, Rajput NS, Viegas J, Jouiad M (2017) Enhanced solar absorption of gold plasmon assisted TiO2-based water splitting composite. Sol Energy Mater Sol Cells 180:1–8. Google Scholar
  51. 51.
    Abed J (2017) Characterization and modification of solar energy water splitting material for storable characterization and modification of solar energy water splitting material for storable fuel generation by Jehad Abed a thesis presented to the. Masdar Institute of Science and TechnologyGoogle Scholar
  52. 52.
    WITec (2017) High-resolution optical and scanning probe microscopy systemsGoogle Scholar
  53. 53.
    Palik ED (1998) Handbook of optical constants of solidsGoogle Scholar
  54. 54.
    Ratzsch S, Kley E-B, Tünnermann A, Szeghalmi A (2015) Influence of the oxygen plasma parameters on the atomic layer deposition of titanium dioxide. Nanotechnology 26:024003. Google Scholar
  55. 55.
    Lide DR (2003) CRC handbook of chemistry and physics. Handb Chem Phys 53:2616. Google Scholar
  56. 56.
    Flageolet B, Villechaise P, Jouiad M, Mendez J (2004) Ageing characterization of the powder metallurgy superalloy N18. Superalloys 2004:371–379Google Scholar
  57. 57.
    Nazirzadeh MA, Atar FB, Turgut BB, Okyay AK (2014) Random sized plasmonic nanoantennas on silicon for low-cost broad-band near-infrared photodetection. Sci Rep 4:7103. Google Scholar
  58. 58.
    Yu K, Tian Y, Tatsuma T (2006) Size effects of gold nanaoparticles on plasmon-induced photocurrents of gold-TiO2 nanocomposites. Phys Chem Chem Phys 8:5417–5420. Google Scholar
  59. 59.
    Bechelany M, Maeder X, Riesterer J, Hankache J, Lerose D, Christiansen S, Michler J, Philippe L (2010) Synthesis mechanisms of organized gold nanoparticles: influence of annealing temperature and atmosphere. Cryst Growth Des 10:587–596. Google Scholar
  60. 60.
    Seguini G, Llamoja Curi J, Spiga S, Tallarida G, Wiemer C, Perego M (2014) Solid-state dewetting of ultra-thin Au films on SiO 2 and HfO 2. Nanotechnology 25:495603. Google Scholar
  61. 61.
    Nsimama PD, Herz A, Wang D, Schaaf P (2016) Influence of the substrate on the morphological evolution of gold thin films during solid-state dewetting. Appl Surf Sci 388:475–482. Google Scholar
  62. 62.
    Niekiel F, Schweizer P, Kraschewski SM, Butz B, Spiecker E (2015) The process of solid-state dewetting of Au thin films studied by in situ scanning transmission electron microscopy. Acta Mater 90:118–132. Google Scholar
  63. 63.
    Nunzi F, De Angelis F, Selloni A (2016) Ab initio simulation of the absorption spectra of photoexcited carriers in TiO2 nanoparticles. J Phys Chem Lett 7:3597–3602. Google Scholar
  64. 64.
    Alsawafta M, Wahbeh M, Van TV (2012) Simulated optical properties of gold nanocubes and nanobars by discrete dipole approximation. J Nanomater 2012:1–9. Google Scholar
  65. 65.
    Mooradian A (1969) Photoluminescence of metals. Phys Rev Lett 22:185–187. Google Scholar
  66. 66.
    Liao H, Wen W, Wong GK (2006) Photoluminescence from Au nanoparticles embedded in Au:oxide composite films. J Opt Soc Am B 23:2518. Google Scholar
  67. 67.
    Beversluis MR, Bouhelier A, Novotny L (2003) Continuum generation from single gold nanostructures through near-field mediated intraband transitions. Phys Rev B 68:115433. Google Scholar
  68. 68.
    Hu H, Duan H, Yang JKW, Shen ZX (2012) Plasmon-modulated photoluminescence of individual gold nanostructures. ACS Nano 6:10147–10155. Google Scholar
  69. 69.
    Zakaria R, Hamdan KS, Noh SMC, Supangat A, Sookhakian M (2015) Surface plasmon resonance and photoluminescence studies of Au and Ag micro-flowers. Opt Mater Express 5:943. Google Scholar
  70. 70.
    Shahbazyan TV (2017) Surface-assisted carrier excitation in plasmonic nanostructures. Plasmonics 13:1–5. Google Scholar
  71. 71.
    Chang W-S, Willingham BA, Slaughter LS, Khanal BP, Vigderman L, Zubarev ER, Link S (2011) Low absorption losses of strongly coupled surface plasmons in nanoparticle assemblies. Proc Natl Acad Sci U S A 108:19879–19884. Google Scholar
  72. 72.
    Chen L, Wei YM, Zang XF, Zhu YM, Zhuang SL (2016) Excitation of dark multipolar plasmonic resonances at terahertz frequencies. Sci Rep 6:1–12. Google Scholar
  73. 73.
    Chen L, Xu N, Singh L, Cui T, Singh R, Zhu Y, Zhang W (2017) Defect-induced Fano resonances in corrugated Plasmonic metamaterials. Adv Opt Mater 5.
  74. 74.
    Kraus T, Malaquin L, Schmid H, Riess W, Spencer ND, Wolf H (2007) Nanoparticle printing with single-particle resolution. Nat Nanotechnol 2:570–576. Google Scholar
  75. 75.
    Klar T, Perner M, Grosse S, von Plessen G, Spirkl W, Feldmann J (1998) Surface-plasmon resonances in single metallic nanoparticles. Phys Rev Lett 80:4249–4252. Google Scholar
  76. 76.
    Bouillard J-S, Vilain S, Dickson W, Zayats a V (2010) Hyperspectral imaging with scanning near-field optical microscopy: applications in plasmonics. Opt Express 18:16513–16519. Google Scholar
  77. 77.
    Denkova D (2016) Optical characterization of plasmonic nanostructures: near-field imaging of the magnetic field of light.
  78. 78.
    Guo J, Ueno K, Yang J et al (2017) Exploring the near-field of strongly coupled waveguide-plasmon modes by plasmon-induced photocurrent generation using a gold nanograting-loaded titanium dioxide photoelectrode. J Phys Chem C.
  79. 79.
    Zuloaga J, Nordlander P (2011) On the energy shift between near-field and far-field peak intensities in localized plasmon systems. Nano Lett 11:1280–1283. Google Scholar
  80. 80.
    Ghosh SK, Pal T (2007) Interparticle coupling effect on the surface plasmon resonance of gold nanoparticles: from theory to applications. Chem Rev 107:4797–4862. Google Scholar
  81. 81.
    Hecht B, Bielefeldt H, Inouye Y, Pohl DW, Novotny L (2006) Facts and artifacts in near-field optical microscopy facts and artifacts in near-field optical. Microscopy 2492:2492–2498. Google Scholar
  82. 82.
    Payne EK, Shuford KL, Park S, Schatz GC, Mirkin CA (2006) Multipole resonances in gold nanorods. J Phys Chem B 110:2150–2154. Google Scholar

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Authors and Affiliations

  1. 1.Department of Mechanical and Materials EngineeringMasdar Institute of Science and Technology - Khalifa UniversityAbu DhabiUnited Arab Emirates

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