journal article·2025-05-28Open access

Monitoring the chemical and structural changes during progressive aqueous alteration of silica thin films deposited by CVD process : accurate thickness loss rates measurements

Farah Inoubli, Babacar Diallo, Konstantina Christina Topka, Raphael Laloo, Emmanuel Veron, Vincent Sarou-Kanian, Brigitte Caussat, Thierry Sauvage, Viviane Turq, Nadia Pellerin

npj Materials Degradation· Volume 9· Issue 1

Abstract

This study investigates the alteration behaviour in aqueous KOH solution (pH 4) of CVD amorphous silica thin films exhibiting different network qualities. The hydrolysis of the networks was elucidated through ERDA (Elastic Recoil Detection Analysis) hydrogen depth profiles acquired throughout the alteration process. Thickness loss rates were successfully calculated showing remarkably low initial rates ranging from 2.5 to 4.8 nm/day, directly correlated with the initial network quality. A minimal rate as low as 0.5 nm/day, comparable to bulk silica performances, was recorded indicating the limited hydration and hydrolysis mechanisms leading to the release of H 4 SiO 4 . These phenomena are occurring with a cyclic hydrolysis–dissolution process. These findings represent the first available dataset on dissolution rates of CVD-deposited silica films. This comprehensive investigation has facilitated the accurate correlation of CVD deposition temperature and, therefore, the network quality of silica films to the chemical and mechanical response to aqueous alteration.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Semiconductor materials and devices · Metal and Thin Film Mechanics · ZnO doping and properties

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (54)

Show source-provided references
1. Dzioba, S. & Rousina, R. Dielectric thin film deposition by electron cyclotron resonance plasma chemical vapor deposition for optoelectronics. J. Vac. Sci. Technol. B. 12, 433–440 (1994).10.1116/1.587140 ↗
2. Chu, T. L. Dielectric Materials in Semiconductor Devices. J. Vac. Sci. Technol. 6, 25–33 (1969).10.1116/1.1492617 ↗
3. Carmona, N., Villegas, M. A. & Fernández Navarro, J. M. Protective silica thin coatings for historical glasses. Thin Solid Films. 458, 121–128 (2004).10.1016/j.tsf.2003.12.064 ↗
4. Kim, R. N. et al. Effect of SiO2 passivation layer on nanoporous Si photocathode under the density of SiO2 passivation layer. Appl. Surf. Sci. 670, 160594 (2024).10.1016/j.apsusc.2024.160594 ↗
5. Puyo, M. et al. Beyond surface nanoindentation: combining static and dynamic nanoindentation to assess intrinsic mechanical properties of chemical vapor deposition amorphous silicon oxide (SiOx) and silicon oxycarbide (SiOxCy) thin films. Thin Solid Films 735, 138844 (2021).10.1016/j.tsf.2021.138844 ↗
6. Ponton, S. et al. Investigation of the densification mechanisms and corrosion resistance of amorphous silica films. J. Non-Cryst. Solids 515, 34–41 (2019).10.1016/j.jnoncrysol.2019.04.005 ↗
7. Dahotre, N. B., Kadolkar, P. & Shah, S. Refractory ceramic coatings: processes, systems and wettability/adhesion. Surf. Interface Anal. 31, 659–672 (2001).10.1002/sia.1092 ↗
8. Crowell, J. E. Chemical methods of thin film deposition: Chemical vapor deposition, atomic layer deposition, and related technologies. J. Vac. Sci. Technol. A. 21, S88–S95 (2003).10.1116/1.1600451 ↗
9. IslamRaja, M. M., Chang, C., McVittie, J. P., Cappelli, M. A. & Saraswat, K. C. Two-precursor model for low-pressure chemical vapor deposition of silicon dioxide from tetraethylorthosilicate. J. Vac. Sci. Technol. B. 11, 720–726 (1993).10.1116/1.586778 ↗
10. Coltrin, M. E., Ho, P., Moffat, H. K. & Buss, R. J. Chemical kinetics in chemical vapor deposition: growth of silicon dioxide from tetraethoxysilane (TEOS). Thin Solid Films 365, 251–263 (2000).10.1016/S0040-6090(99)01059-7 ↗
11. Bhagat, S. D. & Rao, A. V. Surface chemical modification of TEOS based silica aerogels synthesized by two step (acid–base) sol–gel process. Appl. Surf. Sci. 252, 4289–4297 (2006).10.1016/j.apsusc.2005.07.006 ↗
12. Okuyama, K., Fujimoto, T., Hayashi, T. & Adachi, M. Gas-phase nucleation in the tetraethylorthosilicate(TEOS)/O3 APCVD process. AIChE J. 43, 2688–2697 (1997).10.1002/aic.690431313 ↗
13. Skuja, L., Kajihara, K., Hirano, M. & Hosono, H. Oxygen-excess-related point defects in glassy/amorphous SiO2 and related materials. Nucl. Instrum. Methods Phys. Res. B. 286, 159–168 (2012).10.1016/j.nimb.2012.02.038 ↗
14. Horita, S. & Jain, P. Dependences of deposition rate and OH content on concentration of added trichloroethylene in low-temperature silicon oxide films deposited using silicone oil and ozone gas. Jpn. J. Appl. Phys. 57, 03DA02–07DA02 (2018).10.7567/JJAP.57.03DA02 ↗
15. Topka, K. C. et al. Large temperature range model for the atmospheric pressure chemical vapor deposition of silicon dioxide films on thermosensitive substrates. Chem. Eng. Res. Des. 161, 146–158 (2020).10.1016/j.cherd.2020.07.007 ↗
16. Nishiguchi, T. et al. Improvement in chemical-vapor-deposited-SiO2 film properties by annealing with UV-light-excited ozone. Jpn. J. Appl. Phys. 48, 116509 (2009).10.1143/JJAP.48.116509 ↗
17. Diallo, B. et al. Network hydration, ordering and composition interplay of chemical vapor deposited amorphous silica films from tetraethyl orthosilicate. J. Mater. Res. Technol. 13, 534–547 (2021).10.1016/j.jmrt.2021.04.067 ↗
18. Gin, S., Delaye, J. M., Angeli, F. & Schuller, S. Aqueous alteration of silicate glass: state of knowledge and perspectives. npj Mater. Degrad. 5, 42 (2021).10.1038/s41529-021-00190-5 ↗
19. Crundwell, F. K. On the mechanism of the dissolution of quartz and silica in aqueous solutions. ACS Omega 2, 1116–1127 (2017).10.1021/acsomega.7b00019 ↗
20. Qian, Z., Wang, S., Ye, X., Liu, Z. & Wu, Z. Corrosion resistance and wetting properties of silica-based superhydrophobic coatings on AZ31B Mg alloy surfaces. Appl. Surf. Sci. 453, 1–10 (2018).10.1016/j.apsusc.2018.05.086 ↗
21. Pliskin, W. A. Comparison of properties of dielectric films deposited by various methods. J. Vac. Sci. Technol. 14, 1064–1081 (1977).10.1116/1.569413 ↗
22. Klause, M., Rothhaar, U., Bicker, M. & Ohling, W. Dissolution of thin SiO2-coatings—characterization and evaluation. J. Non-Cryst. Solids 356, 141–146 (2010).10.1016/j.jnoncrysol.2009.11.003 ↗
23. Moore, C. et al. Study of Structure and Quality of Different Silicon Oxides Using FTIR and Raman Microscopy. in Proc. of SPIE, Opto-Ireland, Optics and Photonics Technologies and Applications. 4876, 1247–1256 (T. J. Glynn, 2003).10.1117/12.464024 ↗
24. Shaganov, I. I., Perova, T. S., Moore, R. A. & Berwick, K. Spectroscopic characterisation of SiO and SiO2 solid films: assignment and local field influence. J. Mater. Sci. Mater. Electron. 12, 351–355 (2001).10.1023/A:1011256730555 ↗
25. Olsen, J. E. & Shimura, F. Infrared spectroscopy of thin silicon dioxide on silicon. Appl. Phys. Lett. 53, 1934–1936 (1988).10.1063/1.100487 ↗
26. Boyd, I. W. & Wilson, J. I. B. A study of thin silicon dioxide films using infrared absorption techniques. J. Appl. Phys. 53, 4166–4172 (1982).10.1063/1.331239 ↗
27. Lukovsky, G., Mantini, M. J., Srivastava, J. K. & Irene, E. A. Low-temperature growth of silicon dioxide films: a study of chemical bonding by ellipsometry and infrared spectroscopy. J. Vac. Sci. Technol. B5, 530–537 (1987).10.1116/1.583944 ↗
28. Taraskin, S. N. & Elliott, S. R. Nature of vibrational excitations in vitreous silica. Phys. Rev. B. 56, 8605–8622 (1997).10.1103/PhysRevB.56.8605 ↗
29. Harbecke, B., Heinz, B. & Grosse, P. Optical-properties of thin films and the Berreman effect. Appl. Phys. A: Mater. Sci. Process. 38, 263–267 (1985).10.1007/BF00616061 ↗
30. Innocenzi, P. Infrared spectroscopy of sol–gel derived silica-based films: a spectra-microstructure overview. J. Non-Cryst. Solids 316, 309–319 (2003).10.1016/S0022-3093(02)01637-X ↗
31. Milella, A., Palumbo, F., Delattre, J. L., Fracassi, F. & d’Agostino, R. Deposition and characterization of dielectric thin films from allyltrimethylsilane glow discharges. Plasma Process. Polym. 4, 425–432 (2007).10.1002/ppap.200600186 ↗
32. Christy, A. A. & Egeberg, P. K. Quantitative determination of surface silanol groups in silicagel by deuterium exchange combined with infrared spectroscopy and chemometrics. Analyst 130, 738–744 (2005).10.1039/b501895c ↗
33. Oufakir, A. et al. Study of structural short order and surface changes of SiO2 compounds. MATEC Web Conf. 149, 01041 (2018).10.1051/matecconf/201814901041 ↗
34. Innocenzi, P. & Falcaro, P. Order-disorder transitions and evolution of silica structure in self-assembled mesostructured silica films studied through FTIR spectroscopy. J. Phys. Chem. B. 107, 4711–4717 (2003).10.1021/jp026609z ↗
35. Collin, M. et al. Chemical durability of lead crystal glass: comparison of short-term aqueous and atmospheric alteration at 90 °C. Int. J. Appl. Glass Sci. 12, 158–174 (2021).10.1111/ijag.15843 ↗
36. Jedlicka, A. B. & Clare, A. G. Chemical durability of commercial silicate glasses. I material characterization. J. Non-Cryst. Solids 281, 6–21 (2001).10.1016/S0022-3093(00)00442-7 ↗
37. Scholze, H. Glass-water interactions. J. Non-Cryst. Solids 102, 1–10 (1988).10.1016/0022-3093(88)90105-6 ↗
38. Walsh, T. R., Wilson, M. & Sutton, A. P. Hydrolysis of the amorphous silica surface. II. Calculation of activation barriers and mechanisms. J. Chem. Phys. 113, 9191–9201 (2000).10.1063/1.1320057 ↗
39. Pelmenschikov, A., Leszczynski, J. & Pettersson, L. G. M. Mechanism of dissolution of neutral silica surfaces: including effect of self-healing. J. Phys. Chem. A. 105, 9528–9532 (2001).10.1021/jp011820g ↗
40. Dove, P. M., Han, N., Wallace, A. F. & De Yoreo, J. Kinetics of amorphous silica dissolution and the paradox of the silica polymorphs. Proc. Natl. Acad. Sci. USA105, 9903–9908 (2008).10.1073/pnas.0803798105 ↗
41. Moreno, J. A., Garrido, B., Samitier, J. & Morante, J. R. Analysis of geometrical effects on the behavior of transverse and longitudinal modes of amorphous silicon compounds. J. Appl. Phys. 81, 1933–1942 (1997).10.1063/1.364049 ↗
42. De Sousa Meneses, D. et al. Investigation of medium range order in silicate glasses by infrared spectroscopy. Vib. Spectrosc. 65, 50–57 (2013).10.1016/j.vibspec.2012.11.015 ↗
43. Allen, L. H. & Matigevic, E. Stability of colloidal silica: II. Ion exchange. J. Colloid Interface Sci. 33, 420–429 (1970).10.1016/0021-9797(70)90234-1 ↗
44. Almeida, R. M. & Pantano, C. G. Structural investigation of silica gel films by infrared spectroscopy. J. Appl. Phys. 68, 4225–4232 (1990).10.1063/1.346213 ↗
45. Wei, S., Qun-Bo, F., Fu-Chi, W. & Zhuang, M. The influence of defects on the effective Young’s modulus of a defective solid. Chin. Phys. B. 22, 044601 (2013).10.1088/1674-1056/22/4/044601 ↗
46. Kvashnin, A. G., Sorokin, P. B. & Kvashnin, D. G. The theoretical study of mechanical properties of graphene membranes, fullerenes, nanotubes and carbon nanostructures, 18, 497–500 https://doi.org/10.1080/1536383X.2010.488160 (Taylor & Francis, 2010).10.1080/1536383X.2010.488160 ↗
47. Gilman, J. J. Chemistry and physics of mechanical hardness https://doi.org/10.1002/9780470446836 (John Wiley & Sons, 2009).10.1002/9780470446836 ↗
48. Yamane, M. & Mackenzie, J. D. Vicker’s hardness of glass. J. Non-Cryst. Solids 15, 153–164 (1974).10.1016/0022-3093(74)90044-1 ↗
49. Mayer, M. SIMNRA, a simulation program for the analysis of NRA, RBS and ERDA. AIP Conf. Proc. 475, 541–544 (1999).10.1063/1.59188 ↗
50. Cross section 1H(4He,4He)1H Sigmacalc. Online: http://sigmacalc.iate.obninsk.ru/.
51. Martin, G. et al. Accurate automated non-resonant NRA depth profiling: Application to the low 3He concentration detection in UO2 and SiC. Nucl. Instrum. Methods Phys. Res. B. 258, 471–478 (2007).10.1016/j.nimb.2007.01.288 ↗
52. Lange, P. & Windbracke, W. Characterization of thermal and deposited thin oxide layers by longitudinal optical-transverse optical-excitation in Fourier-Transform IR transmission measurements. Thin Solid Films 174, 159–164 (1989).10.1016/0040-6090(89)90885-7 ↗
53. Massiot, D. dmfit program; available at http://crmht-europe.cnrsorleans.fr.
54. Saha, R. & Nix, W. D. Effects of the substrate on the determination of thin film mechanical properties by nanoindentation. Acta Mater. 50, 23–38 (2002).10.1016/S1359-6454(01)00328-7 ↗