Skip to main content Accessibility help
×
Home

Microstructure and dielectric properties with CuO additions to liquid phase sintered BaTiO3 thin films

  • David T. Harris (a1), Matthew J. Burch (a1), Edward J. Mily (a1), Elizabeth C. Dickey (a1) and Jon-Paul Maria (a1)...

Abstract

The refractory nature of BaTiO3 leads to limited densification and grain growth for films processed at low temperatures and a modest nonlinear dielectric response due to a marked sensitivity to physical scale and material quality. Adding liquid-forming sintering aids, common in bulk ceramics, to thin films enhances mass transport, leading to enhanced grain growth at lower temperatures. This work explores the effectiveness of a sputtered CuO buffer layer with BaO–B2O3 (BBO) fluxes to engineer the microstructure of BaTiO3 films. Grain size and homogeneity increase in the presence of even a ∼1 nm CuO layer. In general, grain size increases from 75 to 370 nm with an addition of 2.2% BBO and 8 nm CuO. Room temperature capacitance in fluxed films increases by a factor of 5 over pure films, and ferroelectric phase transitions are clearly observable in dielectric measurements. CuO–BBO proves effective on (0001) Al2O3 and (100) MgO substrates, although all microstructures are notably finer for the latter.

Copyright

Corresponding author

a) Address all correspondence to this author. e-mail: david.harris@wisc.edu

References

Hide All
1. Aygün, S.M., Ihlefeld, J.F., Borland, W.J., and Maria, J-P.: Permittivity scaling in Ba1−x Sr x TiO3 thin films and ceramics. J. Appl. Phys. 109, 034108 (2011).
2. Frey, M.H., Xu, Z., Han, P., and Payne, D.A.: The role of interfaces on an apparent grain size effect on the dielectric properties for ferroelectric barium titanate ceramics. Ferroelectrics 206, 337353 (1998).
3. Shaw, T.M., Suo, Z., Huang, M., Liniger, E., Laibowitz, R.B., and Baniecki, J.D.: The effect of stress on the dielectric properties of barium strontium titanate thin films. Appl. Phys. Lett. 75, 2129 (1999).
4. Streiffer, S.K., Basceri, C., Parker, C.B., Lash, S.E., and Kingon, A.I.: Ferroelectricity in thin films: The dielectric response of fiber-textured (Ba x Sr1−x )Ti1+y O3+z thin films grown by chemical vapor deposition. J. Appl. Phys. 86, 4565 (1999).
5. Arlt, G., Hennings, D., and de With, G.: Dielectric properties of fine-grained barium titanate ceramics. J. Appl. Phys. 58, 1619 (1985).
6. Zhao, Z., Buscaglia, V., Viviani, M., Buscaglia, M., Mitoseriu, L., Testino, A., Nygren, M., Johnsson, M., and Nanni, P.: Grain-size effects on the ferroelectric behavior of dense nanocrystalline BaTiO3 ceramics. Phys. Rev. B: Condens. Matter Mater. Phys. 70, 024107 (2004).
7. Kishi, H., Mizuno, Y., and Chazono, H.: Base-metal electrode-multilayer ceramic capacitors: Past, present and future perspectives. Jpn. J. Appl. Phys. 42, 115 (2003).
8. Prakash, D., Sharma, B.P., Rama Mohan, T.R., and Gopalan, P.: Flux additions in barium titanate: Overview and prospects. J. Solid State Chem. 155, 8695 (2000).
9. Takahashi, R., Yonezawa, Y., Ohtani, M., Kawasaki, M., Nakajima, K., Chikyow, T., Koinuma, H., and Matsumoto, Y.: Perfect Bi4Ti3O12 single-crystal films via flux-mediated epitaxy. Adv. Funct. Mater. 16, 485491 (2006).
10. Ihlefeld, J.F., Borland, W.J., and Maria, J-P.: Enhanced dielectric and crystalline properties in ferroelectric barium titanate thin films. Adv. Funct. Mater. 17, 11991203 (2007).
11. Harris, D.T., Burch, M.J., Ihlefeld, J.F., Lam, P.G., Li, J., Dickey, E.C., and Maria, J-P.: Realizing strain enhanced dielectric properties in BaTiO3 films by liquid phase assisted growth. Appl. Phys. Lett. 103, 012904 (2013).
12. Harris, D.T., Lam, P.G., Burch, M.J., Li, J., Rogers, B.J., Dickey, E.C., and Maria, J-P.: Ultra-high tunability in polycrystalline Ba1−x Sr x TiO3 thin films. Appl. Phys. Lett. 105, 072904 (2014).
13. Burn, I.: Flux-sintered BaTiO3 dielectrics. J. Mater. Sci. 17, 13981408 (1982).
14. Hennings, D. and Schreinemacher, H.: Method of producing a dielectric with perowskite structure and containing a copper oxide, United States Patent Office. U.S. Patent No. US4222885A, 1980.
15. Hennings, D. and Schreinemacher, H.: Method of producing a dielectric with perowskite structure and containing a copper oxide, United States Patent Office. U.S. Patent No. US4244830A, 1981.
16. Li, T., Yang, K., Xue, R., Xue, Y., and Chen, Z.: The effect of CuO doping on the microstructures and dielectric properties of BaTiO3 ceramics. J. Mater. Sci.: Mater. Electron. 22, 838842 (2010).
17. Yang, C-F.: The influence of CuO–BaO mixture addition on the grain growth and dielectric characteristics of BaTiO3 ceramics. Ceram. Interfaces 24, 341346 (1998).
18. ASTM International: ASTM E112-13, Standard Test Methods for Determining Average Grain Size (ASTM International, West Conshohocken, PA, 2013).
19. Zhang, W., Osamura, K., and Ochiai, S.: Phase diagram of the BaO–CuO binary system. J. Am. Ceram. Soc. 73, 19581964 (1990).
20. Levin, E.M. and McMurdie, H.F.: The system BaO–B2O3 . J. Am. Ceram. Soc. 32, 99105 (1949).
21. Burch, M.J., Li, J., Harris, D.T., Maria, J-P., and Dickey, E.C.: Mechanisms for microstructure enhancement in flux-assisted growth of barium titanate on sapphire. J. Mater. Res. 29, 843848 (2014).
22. Harris, D.T., Burch, M.J., Li, J., Dickey, E.C., and Maria, J-P.: Low-temperature control of twins and abnormal grain growth in BaTiO3 . J. Am. Ceram. Soc. 98, 23812387 (2015).
23. Derling, S., Müller, T., and Abicht, H.: Copper oxide as a sintering agent for barium titanate based ceramics. J. Mater. Sci. 36, 14251431 (2001).
24. Lim, J-B., Nahm, S., Kim, H-T., Kim, J-H., Paik, J-H., and Lee, H-J.: Effect of B2O3 and CuO on the sintering temperature and microwave dielectric properties of the BaTi4O9 ceramics. J. Electroceram. 17, 393397 (2006).
25. Kim, M-H., Jeong, Y-H., Nahm, S., Kim, H-T., and Lee, H-J.: Effect of B2O3 and CuO additives on the sintering temperature and microwave dielectric properties of Ba(Zn1/3Nb2/3)O3 ceramics. J. Eur. Ceram. Soc. 26, 21392142 (2006).
26. Gadalla, A.M.M. and White, J.: Equilibrium relationships in the system CuO–Cu2O–Al2O3 . Trans. Br. Ceram. Soc. 63, 57 (1964).
27. McCauley, D., Newnham, R.E., and Randall, C.A.: Intrinsic size effects in a barium titanate glass-ceramic. J. Am. Ceram. Soc. 81, 979987 (1998).
28. Ihlefeld, J.F., Daniels, P.R., Aygün, S.M., Borland, W.J., and Maria, J-P.: Property engineering in BaTiO3 films by stoichiometry control. J. Mater. Res. 25, 10641071 (2010).
29. Lee, J.K., Hong, K.S., and Jang, J.W.: Roles of Ba/Ti ratios in the dielectric properties of BaTiO3 ceramics. J. Am. Ceram. Soc. 84, 20012006 (2001).
30. Lupascu, D.C., Genenko, Y., and Balke, N.: Aging in ferroelectrics. J. Am. Ceram. Soc. 89, 224229 (2006).
31. Tan, Y.Q., Zhang, J.L., and Wang, C.L.: Aging behaviours of CuO modified BaTiO3 ceramics. Adv. Appl. Ceram. 113, 223227 (2014).
32. Langhammer, H.T., Müller, T., Böttcher, R., and Abicht, H-P.: Crystal structure and related properties of copper-doped barium titanate ceramics. Solid State Sci. 5, 965971 (2003).
33. Robels, U. and Arlt, G.: Domain wall clamping in ferroelectrics by orientation of defects. J. Appl. Phys. 73, 3454 (1993).
34. Young, A., Hilmas, G., Zhang, S.C., and Schwartz, R.W.: Effect of liquid-phase sintering on the breakdown strength of barium titanate. J. Am. Ceram. Soc. 90, 15041510 (2007).
35. Wu, Z.H., Liu, H.X., Cao, M.H., Shen, Z.Y., Yao, Z.H., Hao, H., and Luo, D.B.: Effect of BaO–Al2O3–B2O3–SiO2 glass additive on densification and dielectric properties of Ba0.3Sr0.7TiO3 ceramics. J. Ceram. Soc. Jpn. 116, 345349 (2008).
36. Krasevec, V., Drofenik, M., and Kolar, D.: Genesis of the (111) twin in barium titanate. J. Am. Ceram. Soc. 73, 856860 (1990).
37. Krasevec, V., Drofenik, M., and Kolar, D.: Topotaxy between BaTiO3 and Ba6Ti17O40 . J. Am. Ceram. Soc. 70, C-193C-195 (1987).
38. Lee, B., Chung, S., and Kang, S-J.L.: Grain boundary faceting and abnormal grain growth in BaTiO3 . Acta Mater. 48, 15751580 (2000).
39. Lee, B-K. and Kang, S-J.L.L.: Second-phase assisted formation of {111} twins in barium titanate. Acta Mater. 49, 13731381 (2001).
40. Lee, B., Chung, S., and Kang, S.L.: Necessary conditions for the formation of {111} twins in barium titanate. J. Am. Ceram. Soc. 83, 28582860 (2004).
41. DeVRIES, R.C.: Observations on growth of BaTiO3 crystals from KF solutions. J. Am. Ceram. Soc. 42, 547558 (1959).
42. Eibl, O., Pongratz, P., and Skalicky, P.: Crystallography of (111) twins in BaTiO3 . Philos. Mag. Part B 57, 521534 (1988).
43. Eibl, O., Pongratz, P., Skalicky, P., and Schmelz, H.: Formation of (111) twins in BaTiO3 ceramics. J. Am. Ceram. Soc. 70, C-195C-197 (1987).

Keywords

Microstructure and dielectric properties with CuO additions to liquid phase sintered BaTiO3 thin films

  • David T. Harris (a1), Matthew J. Burch (a1), Edward J. Mily (a1), Elizabeth C. Dickey (a1) and Jon-Paul Maria (a1)...

Metrics

Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed