Journal of Materials Science

, Volume 53, Issue 1, pp 727–738 | Cite as

Synthesis and characterization of tin dioxide thick film modified by APTES in vapor and liquid phases

  • Mohamad Hijazi
  • Valérie Stambouli
  • Mathilde RieuEmail author
  • Vincent Barnier
  • Guy Tournier
  • Thomas Demes
  • Jean-Paul Viricelle
  • Christophe Pijolat
Electronic materials


Surface functionalization has numerous applications worldwide. Silicon oxide has been a research material of choice. However, tin dioxide (SnO2) films are employed in many applications especially in gas sensors, and little studied in regard to functionalization. Thus, they were chosen to be functionalized via 3-aminopropyltriethoxysilane (APTES). Different synthesis parameters were tested such as APTES grafting by vapor or liquid phases deposition. In liquid, many parameters were investigated: water presence, reaction times, and APTES concentration. The presence and reactivity of grafted amine-terminated film on SnO2 were carried out by Alexa Fluor® molecules. In addition, APTES grafting was characterized using attenuated total reflectance Fourier transform infrared spectroscopy and X-ray photoelectron spectrometry techniques. These characterizations showed how synthesis parameters affect the amount and thickness of APTES films. Optimal liquid silanization parameters were determined in order to obtain a saturated SnO2 surface with APTES molecules. Importantly, the addition of 5 vol% H2O to the APTES solution provided denser surface coverage, by hydrolyzing the ethoxy groups to silanol. An almost 50% improvement over anhydrous liquid and vapor methods was obtained.


Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Le M, Jimenez C, Chainet E, Stambouli V (2015) A label-free impedimetric DNA sensor based on a nanoporous SnO2 film: fabrication and detection performance. Sensors 15:10686–10704CrossRefGoogle Scholar
  2. 2.
    Stambouli V, Labeau M, Matko I et al (2006) Development and functionalisation of Sb doped SnO2 thin films for DNA biochip applications. Sens Actuators B Chem 113:1025–1033CrossRefGoogle Scholar
  3. 3.
    Garg N, Mohanty A, Lazarus N et al (2010) Robust gold nanoparticles stabilized by trithiol for application in chemiresistive sensors. Nanotechnology 21:405501CrossRefGoogle Scholar
  4. 4.
    Matsubara I, Hosono K, Murayama N et al (2005) Organically hybridized SnO2 gas sensors. Sens Actuators B Chem 108:143–147CrossRefGoogle Scholar
  5. 5.
    Wang B, Haick H (2013) Effect of functional groups on the sensing properties of silicon nanowires toward volatile compounds. ACS Appl Mater Interfaces 5:2289–2299CrossRefGoogle Scholar
  6. 6.
    Cecchetto L, Denoyelle A, Delabouglise D, Petit J-P (2008) A silane pre-treatment for improving corrosion resistance performances of emeraldine base-coated aluminium samples in neutral environment. Appl Surf Sci 254:1736–1743CrossRefGoogle Scholar
  7. 7.
    Ruckenstein E, Li Z (2005) Surface modification and functionalization through the self-assembled monolayer and graft polymerization. Adv Colloid Interface Sci 113:43–63CrossRefGoogle Scholar
  8. 8.
    Hoffmann MWG, Mayrhofer L, Casals O et al (2014) A highly selective and self-powered gas sensor via organic surface functionalization of p-Si/n-ZnO diodes. Adv Mater 26:8017–8022CrossRefGoogle Scholar
  9. 9.
    Klug J, Pérez LA, Coronado EA, Lacconi GI (2013) Chemical and electrochemical oxidation of silicon surfaces functionalized with APTES: the role of surface roughness in the AuNPs anchoring kinetics. J Phys Chem C 117:11317–11327CrossRefGoogle Scholar
  10. 10.
    Ben Haddada M, Blanchard J, Casale S et al (2013) Optimizing the immobilization of gold nanoparticles on functionalized silicon surfaces: amine- vs thiol-terminated silane. Gold Bull 46:335–341CrossRefGoogle Scholar
  11. 11.
    Herzer N, Hoeppener S, Schubert US (2010) Fabrication of patterned silane based self-assembled monolayers by photolithography and surface reactions on silicon-oxide substrates. Chem Commun 46:5634CrossRefGoogle Scholar
  12. 12.
    Pujari SP, Scheres L, Marcelis ATM, Zuilhof H (2014) Covalent surface modification of oxide surfaces. Angew Chem Int Ed 53:6322–6356CrossRefGoogle Scholar
  13. 13.
    Zhang F, Sautter K, Larsen AM et al (2010) Chemical vapor deposition of three aminosilanes on silicon dioxide: surface characterization, stability, effects of silane concentration, and cyanine dye adsorption. Langmuir 26:14648–14654CrossRefGoogle Scholar
  14. 14.
    Puleo DA (1996) Retention of enzymatic activity immobilized on silanized Co–Cr–Mo and Ti–6Al–4V, vol 97. Wiley, Hoboken, pp 222–228Google Scholar
  15. 15.
    Shehada N, Brönstrup G, Funka K et al (2015) Ultrasensitive silicon nanowire for real-world gas sensing: noninvasive diagnosis of cancer from breath volatolome. Nano Lett 15:1288–1295CrossRefGoogle Scholar
  16. 16.
    Fiorilli S, Rivolo P, Descrovi E et al (2008) Vapor-phase self-assembled monolayers of aminosilane on plasma-activated silicon substrates. J Colloid Interface Sci 321:235–241CrossRefGoogle Scholar
  17. 17.
    Kim J, Seidler P, Wan LS, Fill C (2009) Formation, structure, and reactivity of amino-terminated organic films on silicon substrates. J Colloid Interface Sci 329:114–119CrossRefGoogle Scholar
  18. 18.
    Acres RG, Ellis AV, Alvino J et al (2012) Molecular structure of 3-aminopropyltriethoxysilane layers formed on silanol-terminated silicon surfaces. J Phys Chem C 116:6289–6297CrossRefGoogle Scholar
  19. 19.
    Aissaoui N, Bergaoui L, Landoulsi J et al (2012) Silane layers on silicon surfaces: mechanism of interaction, stability, and influence on protein adsorption. Langmuir 28:656–665CrossRefGoogle Scholar
  20. 20.
    Gourari H, Lumbreras M, Van Landschoot R, Schoonman J (1998) Elaboration and characterization of SnO2–Mn2O3 thin layers prepared by electrostatic spray deposition. Sens Actuators B Chem 47:189–193CrossRefGoogle Scholar
  21. 21.
    Chen JS, Lou XWD (2013) SnO2-based nanomaterials: synthesis and application in lithium-ion batteries. Small 9:1877–1893CrossRefGoogle Scholar
  22. 22.
    Tournier G, Pijolat C (2005) Selective filter for SnO2-based gas sensor: application to hydrogen trace detection. Sens Actuators B Chem 106:553–562CrossRefGoogle Scholar
  23. 23.
    Chiang C-H, Ishida H, Koenig JL (1980) The structure of γ-aminopropyltriethoxysilane on glass surfaces. J Colloid Interface Sci 74:396–404CrossRefGoogle Scholar
  24. 24.
    Tan G, Zhang L, Ning C et al (2011) Preparation and characterization of APTES films on modification titanium by SAMs. Thin Solid Films 519:4997–5001CrossRefGoogle Scholar
  25. 25.
    Wen K, Maoz R, Cohen H et al (2008) Postassembly chemical modification of a highly ordered organosilane multilayer: new insights into the structure, bonding, and dynamics of self-assembling silane monolayers. ACS Nano 2:579–599CrossRefGoogle Scholar
  26. 26.
    Rozlosnik N, Gerstenberg MC, Larsen NB (2003) Effect of solvents and concentration on the formation of a self-assembled monolayer of octadecylsiloxane on silicon (001). Langmuir 19:1182–1188CrossRefGoogle Scholar
  27. 27.
    Pasternack RM, Rivillon Amy S, Chabal YJ (2008) Attachment of 3-(Aminopropyl)triethoxysilane on silicon oxide surfaces: dependence on solution temperature. Langmuir 24:12963–12971CrossRefGoogle Scholar
  28. 28.
    Wang B, Cancilla JC, Torrecilla JS, Haick H (2014) Artificial sensing intelligence with silicon nanowires for ultraselective detection in the gas phase. Nano Lett 14:933–938CrossRefGoogle Scholar
  29. 29.
    Tougaard S (2003) QUASES: software for quantitative XPS/AES of surface nano-structures by analysis of the peak shape and background (version 5.0). QUASES-Tougaard Inc Odense Den.
  30. 30.
    Tougaard S (1997) Universality classes of inelastic electron scattering cross-sections. Surf Interface Anal 25:137–154CrossRefGoogle Scholar
  31. 31.
    Tanuma S, Powell CJ, Penn DR (1993) Calculations of electron inelastic mean free paths (IMFPS). IV. Evaluation of calculated IMFPs and of the predictive IMFP formula TPP-2 for electron energies between 50 and 2000 eV. Surf Interface Anal 20:77–89CrossRefGoogle Scholar
  32. 32.
    Cumpson PJ (2001) Estimation of inelastic mean free paths for polymers and other organic materials: use of quantitative structure–property relationships. Surf Interface Anal 31:23–34CrossRefGoogle Scholar
  33. 33.
    Bicerano J (1996) Prediction of polymer properties, 2nd edn. New York, Marcel DekkerGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2017

Authors and Affiliations

  • Mohamad Hijazi
    • 1
  • Valérie Stambouli
    • 2
  • Mathilde Rieu
    • 1
    Email author
  • Vincent Barnier
    • 1
  • Guy Tournier
    • 1
  • Thomas Demes
    • 2
  • Jean-Paul Viricelle
    • 1
  • Christophe Pijolat
    • 1
  1. 1.École Nationale Supérieure des Mines, SPIN-EMSE, CNRS, UMR5307, LGFSaint-ÉtienneFrance
  2. 2.LMGP, Université Grenoble-Alpes, Grenoble INP-MINATECGrenoble Cedex 1France

Personalised recommendations