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Fracture of nanoporous methyl silsesquioxane thin-film glasses

  • Eric P. Guyer (a1), Matthias Patz (a2) and Reinhold H. Dauskardt (a1)

The fracture of nanoporous methylsilsesquioxane thin-film glasses in moist air and aqueous solutions was investigated. We demonstrate the effects of controlled volume fractions of nanometer sized pores on the films resistance to fracture. Subcritical cracking accelerated by the presence of moisture, controlled pH, and hydrogen peroxide solutions is reported. Surprising changes in the near threshold growth rate behavior were observed for buffered solutions. We demonstrate that these changes are related to the unexpected diffusion of the aqueous solutions into the highly hydrophobic films. The presence of the solution changes the surface stress of the internal pore surfaces, which changes the stress state of the film. The change in film stress surrounding the crack alters the crack driving force and has profound effects on the resulting crack-growth threshold behavior.

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1.Desai T., Hansford D., Leoni L., Essenpreis M., Ferrari M.: Nanoporous anti-fouling silicon membranes for biosensor applications. Biosens. Bioelectron. 15(9–10), 453 (2000).
2.Cheetham A.K., Ferey G., Loiseau T.: Open-framework inorganic materials. Angew. Chem. Int. Ed. 38, 3269 (1999).
3.Dabrowski A.: Adsorption—From theory to practice. Adv. Colloid Interf. Sci. 93(1–3), 135 (2001).
4.Coakley K.M., McGehee M.D.: Photovoltaic cells made from conjugated polymers infiltrated into mesoporous titania. Appl. Phys. Lett. 83, 3380 (2003).
5.Nguyen C.V., Carter K.R., Hawker C.J., Hedrick J.L., Jaffe R.L., Miller R.D., Remenar J.F., Rhee H.W., Rice P.M., Toney M.F., Trollsas M., Yoon D.Y.: Low-dielectric, nanoporous organosilicate films prepared via inorganic/organic polymer hybrid templates. Chem. Mater. 11, 3080 (1999).
6.Hedrick J.L., Miller R.D., Hawker C.J., Carter K.R., Volksen W., Yoon D.Y., Trollsas M.: Templating nanoporosity in thin-film dielectric insulators. Adv. Mater. 10, 1049 (1998).
7.Iacopi F., Patz M., Vos I., Tokei Z., Sijmus B., Le Q., Sleeckx E., Eyckens B., Struyf H., Das A., Maex K.: Impact of LKD5109 low-k to cap/liner interfaces in single damascene process and performance. Microelectron. Eng. 70(2/4), 293 (2003).
8.Cook R., Liniger E.: Stress-corrosion cracking of low-dielectric constant spin-on-glass thin films. J. Electrochem. Soc. 146, 4439 (1999).
9.Wiederhorn S.M.: Influence of water vapor on crack propagation in soda-lime glass. J. Am. Ceram. Soc. 50, (8), 407 (1967).
10.Lane M.W., Snodgrass J.M., Dauskardt R.H.: Environmental effects on interfacial adhesion. Microelectron. Reliab. 41(9–10), 1615 (2001).
11.Guyer E.P., Dauskardt R.H.: Effect of solution pH on subcritical crack growth in low-k dielectric thin-films. J. Mater. Res. 20, 680687(2005).
12.Vlassak J.J., Lin Y., Tsui T.Y.: Fracture of organosilicate glass thin films: environmental effects. Mater. Sci. Eng. A 391, 159 (2004).
13.Guyer E.P., Dauskardt R.H.: Fracture of nanoporous thin-film glasses. Nat. Mater. 3(1), 53 (2004).
14.Das A., Le Q.T., Furukawa Y., Nguyen V.H., Terzieva V., de Theije F., Whelan C.M., Maenhoudt M., Struyf H., Tokei Z., Iacopi F., Stucchi M., Carbonell L., Vos I., Bender H., Patz M., Beyer G., Van Hove M., Maex K.: Characterisation of JSR's spin-on hardmask FF-02. Microelectron. Eng. 70(2/4), 306 (2003).
15.Lane M., Dauskardt R.H., Vainchtein A., Gao H.: Plasticity contributions to interface adhesion in thin-film interconnect structures. J. Mater. Res. 15, 2758 (2000).
16.Kook S.Y., Dauskardt R.H.: Moisture-assisted subcritical debonding of a polymer/metal interface. J. Appl. Phys. 91, 1293 (2002).
17.Dauskardt R.H., Lane M., Ma Q., Krishna N.: Adhesion and debonding of multi-layer thin film structures. Eng. Fract. Mech. 61(1), 141 (1998).
18.Hohlfelder R.J., Maidenberg D.A., Dauskardt R.H., Wei Y.G., Hutchinson J.W.: Adhesion of benzocyclobutene-passivated silicon in epoxy layered structures. J. Mater. Res. 16, 243 (2001).
19.Rim J. and Dauskardt R.H. (2004, unpublished).
20.Maidenberg D.A., Volksen W., Miller R.D., Dauskardt R.H.: Toughening of nanoporous glasses using porogen residuals. Nat. Mater. 3(7), 464 (2004).
21.Gibson L.J., Ashby M.F.: Cellular Solids: Structure and Properties (Pergamon Press, New York, 1988).
22.Zwissler J.G., Adams M.A.: Stress-corrosion degradation of a developmental aluminoborosilicate cellular glass. J. Metals 33(9), A41 (1981).
23.Cook R.F., Liniger E.G.: Kinetics of indentation cracking in glass. J. Am. Ceram. Soc. 76, 1096 (1993).
24.Lane M.W., Liu X.H., Shaw T.M.: Environmental effects on cracking and delamination of dielectric films. IEEE Trans. Dev. Mater. Reliab. 4(2), 142 (2004).
25.Lin E.K., Lee H.J., Lynn G.W., Wu W.L., O’Neill M.L.: Structural characterization of a porous low-dielectric constant thin film with a non-uniform depth profile. Appl. Phys. Lett. 81(4), 607 (2002).
26.Lane M., Ware R., Voss S., Ma Q., Fujimoto H., Dauskardt R.H.: Progressive debonding of multilayer interconnect structures, in Materials Reliability in Microelectronics VII, edited by Clement J.J., Keller R.R., Krisch K.S., Sanchez J.E., Jr., and Z. Suo (Mater. Res. Soc. Symp. Proc. 473 Pittsburgh, PA, 1997), p. 21.
27.Evans A.G., Hutchinson J.W.: Effects of non-planarity on the mixed-mode fracture resistance of bimaterial interfaces. Acta Metall. 37, 909 (1989).
28.Lawn B.R. Fracture of Brittle Solids (Cambridge University Press, Cambridge, UK, 1993).
29.Kanninen M.F.: Augmented double cantilever beam model for studying crack-propagation and arrest. Int. J. Fract. 9(1), 83 (1973).
30.Strohband S. and Dauskardt R.H., Effect of barrier layer properties on adhesion in thin-film structures. (unpublished).
31.Lane M., Ni W., Dauskardt R.H., Ma Q., Fujimoto H., and Krishna N.: Effects of interface nonplanarity on the interface fracture energy of the TiN/SiO2 system, in Thin-Films—Stresses and Mechanical Properties VII, edited by Cammarata R.C., Nastasi M., Busso E.P., and Oliver W.C. (Mater. Res. Soc. Symp. Proc. 505 Warrendale, PA, 1998), p. 357.
32.Wiederhorn S.M., Johnson H.: Effect of electrolyte pH on crack propagation in glass. J. Am. Ceram. Soc. 56(4), 192 (1973).
33.Wiederhorn S.M., Bolz L.H.: Stress corrosion and static fatigue of glass. J. Am. Ceram. Soc. 53(10), 543 (1970).
34.Michalske T.A., Bunker B.C., Keefer K.D.: Mechanical-properties and adhesion of hydrated glass-surface layers. J. Non-Cryst. Solids 120(1–3), 126 (1990).
35.Dyer T.W.: Moisture instability of borophosphosilicate glass and effects of thermal treatment. J. Electrochem. Soc. 145, 3950 (1998).
36.McInemey E.J. and Flinn P.A.: IEEE Proc. 20th Intern. Reliability Physics, 1979, 111, New York.
37.Guyer E.P. and Dauskardt R.H.: Diffusion of aqueous solutions into hydrophobic nanoporous thin-films (2005, unpublished).
38.Gibbs J.W.: On the equilibrium of heterogeneous substances. Trans. Connect. Acad. Sci. 3, 108 (1876).
39.Nix W.D. private communication, Stanford University (2005).
40.Huang E., Toney M.F., Volksen W., Mecerreyes D., Brock P., Kim H.C., Hawker C.J., Hedrick J.L., Lee V.Y., Magbitang T., Miller R.D., Lurio L.B.: Pore-size distributions in nanoporous methyl silsesquioxane films as determined by small angle x-ray scattering. Appl. Phys. Lett. 81(12), 2232 (2002).
41.Shamiryan D., Abell T., Le Q.T., Maex K.: Pinhole density measurements of barriers deposited on low-k films. Microelectron. Eng. 70(2/4), 341 (2003).
42.Shaw T.M., Jimerson D., Haders D., Murray C.E., Grill A., Edelstein D.C., and Chidambarrao D.: Moisture and oxygen uptake in low k/copper interconnect structures, in Advanced Metallization Conference 2003 (AMC 2003), edited by Ray G.W., Smy T., Ohta T., and Tsujimura M. (Mater. Res. Soc., Warrendale, PA, 2004), p. 77.
43.Worsley M.A., Bent S.F., Gates S.M., Shaw T., Volksen W., Miller R.D.: Microelectron. Eng. 82(2), 113118(2005).
44.McMeeking R., Evans A.: Mechanics of transformation-toughening in brittle materials. J. Am. Ceram. Soc. 65(5), 242 (1982).
45.Budiansky B., Hutchinson J.W., Lambropoulous J.C.: Continuum theory of dilatent transformation toughening in ceramics. Int. J. Solids Struct. 19(4), 337 (1983).
46.Hutchinson J.W.: Crack tip shielding by micro-cracking in brittle solids. Acta Metall. 35, 1605 (1987).
47.Marshall D.B., Shaw M.C., Dauskardt R.H., Ritchie R.O., Readey M.J., Heuer A.H.: Crack-tip transformation zones in toughened zirconia. J. Am. Ceram. Soc. 73, 2659 (1990).
48.Lawn B.R.: Interfacial forces and the fundamental nature of brittle cracks. Appl. Phys. Lett. 47, 809 (1985).
49.Wiederhorn S.M., Fuller E.R.: Effect of surface forces on subcritical crack-growth in glass. J. Am. Ceram. Soc. 72, 248 (1989).
50.Israelachvili J.N., Pashley R.M.: Measurement of the hydrophobic interaction between 2 hydrophobic surfaces in aqueous-electrolyte solutions. J. Colloid Interface Sci. 98, 500 (1984).
51.Vigil G., Xu Z.H., Steinberg S., Israelachvili J.: Interactions of silica surfaces. J. Colloid Interface Sci. 165, 367 (1994).
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