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In situ methods to explore microstructure evolution in chemically derived oxide thin films

Published online by Cambridge University Press:  31 January 2011

Seymen M. Aygün ,
Patrick Daniels ,
William J. Borland  and
Jon-Paul Maria
Patrick Daniels
Affiliation:
Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695
William J. Borland
Affiliation:
DuPont Electronic Technologies, Research Triangle Park, North Carolina 27707
Jon-Paul Maria
Affiliation:
Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695
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Abstract

In situ residual gas analyzer techniques were used to identify process-property relationships that regulate microstructure evolution in chemical solution-deposited BaTiO3 films. In situ analysis of furnace exhaust gasses enabled quantitative exploration of thermolysis and crystallization reactions and an ability to identify processing parameters that influence the temperature ranges over which they occur. The atmospheric analysis was instrumental in identifying heat treatments that produced optimally consolidated precursor gels that crystallized into BaTiO3 layers with optimized structure and properties. Slow ramp rates resulted in higher porosity, larger grain size, and a dramatic drop in the capacitor yield. Fast ramp rates produced similar trends; however, the mechanisms were distinct. The effects of oxygen partial pressure were also explored. BaTiO3 grain size increased with increasing pO2, whereas there was no appreciable influence on density and capacitor yield. Optimal firing parameters, i.e., 20 °C/min ramp rate at a pO2 of 10−13 atm, were identified as those that produced an overlap in the temperature ranges of thermolysis and crystallization reactions and thus a precursor gel with a density and compliance that supports crystallization and densification while tolerating the associated volume contraction. This in situ approach to analyze downstream furnace gas is shown to be a generically applicable means to understand synthesis methods that are complicated by simultaneous mechanisms of precursor decomposition, extraction of volatile components, and crystallization.

Keywords

FerroelectricitySolution depositionDielectric properties
Type
Articles
Information
Journal of Materials Research , Volume 25 , Issue 3 , March 2010 , pp. 427 - 436
Copyright
Copyright © Materials Research Society 2010

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References

REFERENCES

1.Clabaugh, W.S., Swiggard, E.M., Gilchrist, R.Preparation of barium titanyl oxalate tetrahydrate for conversion to barium titanate of high purity J. Res. Natl. Inst. Stand. Technol 56, (5)289 (1956)CrossRefGoogle Scholar
2.Mazdiyasni, K.S., Dolloff, R.T., Smith, J.S.Preparation of high purity submicron titanate powder Am. Ceram. Soc. Bull 48, (4)509 (1969)Google Scholar
3.Pechini, M. U.S. Patent No. 3330697 (1967)Google Scholar
4.Phule, P.P., Risbud, S.H.Low-temperature synthesis and processing of electronic materials in the BaO-TiO2 system J. Mater. Sci 25, (2B)1169 (1990)CrossRefGoogle Scholar
5.Yanovskaya, M.I., Turova, N.Y., Turevskaya, E.P., Novoselova, A.V., Venetsev, Y.N., Sagitov, S.I., Soboleva, E.M.Preparation of ferroelectric barium-titanate films from solutions of metal alcoholates Inorg. Mater 17, (2)221 (1981)Google Scholar
6.Frey, M.H., Payne, D.A.Synthesis and processing of barium-titanate ceramics from alkoxide solutions and monolithic gels Chem. Mater 7, (1)123 (1995)CrossRefGoogle Scholar
7.Gust, M.C., Evans, N.D., Momoda, L.A., Mecartney, M.L.In situ transmission electron microscopy crystallization studies of sol-gel-derived barium titanate thin films J. Am. Ceram. Soc 80, (11)2828 (1997)CrossRefGoogle Scholar
8.Jang, S.I., Choi, B.C., Jang, H.M.Phase-formation kinetics of xerogel and electrical properties of sol-gel-derived BaxSr1-xTiO3 thin films J. Mater. Res 12, (5)1327 (1997)CrossRefGoogle Scholar
9.Kirby, K.W.Alkoxide synthesis techniques for BaTiO3 Mater. Res. Bull. 23, (6)881 (1988)CrossRefGoogle Scholar
10.Gopalakrishnamurthy, H.S., Rao, M.S., Kutty, T.R.N.Thermal-decomposition of titanyl oxalates. 1. Barium titanyl oxalate J. Inorg. Nucl. Chem 37, (4)891 (1975)CrossRefGoogle Scholar
11.Kumar, S., Messing, G.L., White, W.B.Metal-organic resin derived barium-titanate. 1. Formation of barium titanium oxycarbonate intermediate J. Am. Ceram. Soc 76, (3)617 (1993)CrossRefGoogle Scholar
12.Shaikh, A.S., Vest, G.M.Kinetics of BaTiO3 and PbTiO3 formation from metalloorganic precursors J. Am. Ceram. Soc 69, (9)682 (1986)CrossRefGoogle Scholar
13.Stockenhuber, M., Mayer, H., Lercher, J.A.Preparation of barium titanates from oxalates J. Am. Ceram. Soc 76, (5)1185 (1993)CrossRefGoogle Scholar
14.Hasenkox, U., Hoffmann, S., Waser, R.Influence of precursor chemistry on the formation of MTiO3 (M = Ba, Sr) ceramic thin films J. Sol-Gel Sci. Technol 12, (2)67 (1998)CrossRefGoogle Scholar
15.Hoffmann, S., Waser, R.Control of the morphology of CSD-prepared (Ba,Sr)TiO3 thin films J. Eur. Ceram. Soc 19, (6–7)1339 (1999)CrossRefGoogle Scholar
16.Phule, P.P., Risbud, S.H.Sol-gel synthesis of barium-titanate powders using barium acetate and titanium(IV) isopropoxide Adv. Ceram. Mater 3, (2)183 (1988)CrossRefGoogle Scholar
17.Schwartz, R.W., Clem, P.G., Voigt, J.A., Byhoff, E.R., Stry, M.V., Headley, T.J., Missert, N.A.Control of microstructure and orientation in solution-deposited BaTiO3 and SrTiO3 thin films J. Am. Ceram. Soc. 82, (9)2359 (1999)CrossRefGoogle Scholar
18.Brinker, C.J., Scherer, G.W.Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing (Academic Press, Boston 1990)908Google Scholar
19.Schwartz, R.W., Schneller, T., Waser, R.Chemical solution deposition of electronic oxide films C.R. Chim 7, (5)433 (2004)CrossRefGoogle Scholar
20.Tuchiya, T., Kawano, T., Sei, T., Hatano, J.Preparation of ferroelectric BaTiO3 films by sol-gel process and dielectric properties J. Ceram. Soc. Jpn 98, (8)743 (1990)CrossRefGoogle Scholar
21.Dawley, J.T., Clem, P.G.Dielectric properties of random and < 100 > oriented SrTiO3 and (Ba,Sr)TiO3 thin films fabricated on < 100 > nickel tapes Appl. Phys. Lett 81, (16)3028 (2002)CrossRefGoogle Scholar
22.Ihlefeld, J., Laughlin, B., Hunt-Lowery, A., Borland, W., Kingon, A., Maria, J-P.Copper compatible barium titanate thin films for embedded passives J. Electroceram 14, (2)95 (2005)CrossRefGoogle Scholar
23.Ihlefeld, J.F., Maria, J-P., Borland, W.Dielectric and microstructural properties of barium titanate zirconate thin films on copper substrates J. Mater. Res 20, (10)2838 (2005)CrossRefGoogle Scholar
24.Aygun, S.M., Daniels, P., Borland, W., Maria, J-P.Hot sputtering of barium strontium titanate on nickel foils J. Appl. Phys 103, (8)084123 (2008)CrossRefGoogle Scholar
25.Ihlefeld, J.F., Vodnick, A.M., Baker, S.P., Borland, W.J., Maria, J-P.Extrinsic scaling effects on the dielectric response of ferroelectric thin films J. Appl. Phys 103, (7)074112 (2008)CrossRefGoogle Scholar
26.Dechakupt, T., Yang, G., Randall, C.A., Reaney, I.M., Troiler-McKinstry, S.Chemical solution-deposited BaTiO3 thin films on Ni foils: Microstructure and interfaces J. Am. Ceram. Soc. 91, (6)1845 (2008)CrossRefGoogle Scholar
27.Frey, M.H. Grain size effect on structure and properties for chemically prepared barium titanate Ph.D. Thesis University of Illinois at Urbana-Champaign (1996) 206Google Scholar
28.Keddie, J.L., Giannelis, E.P.Effect of heating rate on the sintering of titanium-dioxide thin-films—Competition between densification and crystallization J. Am. Ceram. Soc 74, (10)2669 (1991)CrossRefGoogle Scholar
29.Keddie, J.L., Braun, P.V., Giannelis, E.P.Interrelationship between densification, crystallization, and chemical evolution in sol-gel titania thin-films J. Am. Ceram. Soc 77, (6)1592 (1994)CrossRefGoogle Scholar
30.Scherer, G.W.Sintering of sol-gel films J. Sol-Gel Sci. Technol. 8, (1–3)353 (1997)CrossRefGoogle Scholar
31.Polotai, A.V., Yang, G-Y., Dickey, E.C., Randall, C.A.Utilization of multiple-stage sintering to control Ni electrode continuity in ultrathin Ni-BaTiO3 multilayer capacitors J. Am. Ceram. Soc 90, (12)3811 (2007)CrossRefGoogle Scholar
32.Polotai, A.V., Fujii, I., Shay, D.P., Yang, G-Y., Dickey, E.C., Randall, C.A.Effect of heating rates during sintering on the electrical properties of ultra-thin Ni-BaTiO3 multilayer ceramic capacitors J. Am. Ceram. Soc 91, (8)2540 (2008)CrossRefGoogle Scholar