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Control of octahedral connectivity in perovskite oxide heterostructures: An emerging route to multifunctional materials discovery

Published online by Cambridge University Press:  12 March 2012

James M. Rondinelli
Materials Science and Engineering Department, Drexel University;
Steven J. May
Materials Science and Engineering Department, Drexel University;
John W. Freeland
-X-ray Science Division, Argonne National Laboratory, USA;
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Research in ABO3 perovskite oxides ranges from fundamental scientific studies in superconductivity and magnetism to technologies for advanced low-power electronics, energy storage, and conversion. The breadth in functionalities observed in this versatile materials class originates, in part, from the ability to control the local and extended crystallographic structure of corner-connected octahedral units. While an established paradigm exists to alter the size, shape, and connectivity of the octahedral building blocks in bulk materials, these approaches are often limited to certain subsets of the allowed perovskite archetypes and chemistries. In this article, we describe emerging routes in thin films and multilayer superlattices enabled by epitaxial synthesis aimed at engineering the octahedral connectivity—rotational magnitudes and patterns—to reach unexplored portions of the crystallographic structure–property phase space for rational materials design. We review three promising chemistry-independent strategies that provide a handle to tune the octahedral connectivity: epitaxial strain, interfacial control at perovskite/perovskite heterojunctions, and rotation engineering in short-period superlattices. Finally, we touch upon potential new functionalities that could be attained by extending these approaches to static and dynamic manipulation of the perovskite structure through external fields and highlight unresolved questions for the deterministic control of octahedral rotations in perovskite-structured materials.

Research Article
Copyright © Materials Research Society 2012

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1.Kanis, D.R., Ratner, M.A., Marks, T.J., Chem. Rev. 94, 195 (1994).CrossRefGoogle Scholar
2.Hoffmann, R., Solids and Surfaces: A Chemist’s View of Bonding in Extended Structures (VCH, New York, 1988).CrossRefGoogle Scholar
3.Goodenough, J.B., Rep. Prog. Phys. 67, 1915 (2004).CrossRefGoogle Scholar
4.Salamon, M.B., Jaime, M., Rev. Mod. Phys. 73, 583 (2001).CrossRefGoogle Scholar
5.Imada, M., Fujimori, A., Tokura, Y., Rev. Mod. Phys. 70, 1039 (1998).CrossRefGoogle Scholar
6.Goodenough, J.B., J. Appl. Phys. 37, 1415 (1966).CrossRefGoogle Scholar
7.Zaanen, J., Sawatzky, G.A., Allen, J.W., Phys. Rev. Lett. 55, 418 (1985).CrossRefGoogle Scholar
8.Mazin, I.I., Khomskii, D.I., Lengsdorf, R., Alonso, J.A., Marshall, W.G., Ibberson, R.A., Podlesnyak, A., Martinez-Lope, M.J., Abd-Elmeguid, M.M., Phys. Rev. Lett. 98, 176406 (2007).CrossRefGoogle Scholar
9.Takeda, T., Kanno, R., Kawamoto, Y., Takano, M., Kawasaki, S., Kamiyama, T., Izumi, F., Solid State Sci. 2, 673 (2000).CrossRefGoogle Scholar
10.Woodward, P.M., Cox, D.E., Moshopoulou, E., Sleight, A.W., Morimoto, S., Phys. Rev. B 62, 844 (2000).CrossRefGoogle Scholar
11.Jahn, H.A., Teller, E., Proc. R. Soc. London, Ser. A 161, 220 (1937).CrossRefGoogle Scholar
12.Goodenough, J.B., Annu. Rev. Mater. Sci. 28, 1 (1998).CrossRefGoogle Scholar
13.Lufaso, M.W., Woodward, P.M., Acta Crystallogr., Sect. B: Struct. Sci. 60, 10 (2004).CrossRefGoogle Scholar
14.Burdett, J.K., Inorg. Chem. 20, 1959 (1981).CrossRefGoogle Scholar
15.Kunz, M., Brown, I.D., J. Solid State Chem. 115, 395 (1995).CrossRefGoogle Scholar
16.Halasyamani, P.S., Poeppelmeier, K.R., Chem. Mater. 10, 2753 (1998).CrossRefGoogle Scholar
17.Howard, C.J., Stokes, H.T., Acta Crystallogr., Sect. B: Struct. Sci. 54, 782 (1998).CrossRefGoogle Scholar
18.Stokes, H.T., Kisi, E.H., Hatch, D.M., Howard, C.J., Acta Crystallogr., Sect. B: Struct. Sci. 58, 934 (2002).CrossRefGoogle Scholar
19.Glazer, A.M., Acta Crystallogr., Sect. B: Struct. Sci. 28, 3384 (1972).CrossRefGoogle Scholar
20.Eng, H.W., Barnes, P.W., Auer, B.M., Woodward, P.M., J. Solid State Chem. 175, 94 (2003).CrossRefGoogle Scholar
21.Wang, Y., Sui, Y., Ren, P., Wang, L., Wang, X.J., Su, W.H., Fan, H.J., Inorg. Chem. 49, 3216 (2010).CrossRefGoogle Scholar
22.Anderson, P.W., Phys. Rev. 79, 350 (1950).CrossRefGoogle Scholar
23.Goodenough, J.B., Phys. Rev. 100, 564 (1955).CrossRefGoogle Scholar
24.Kanamori, J., J. Appl. Phys. 31, 14S (1960).CrossRefGoogle Scholar
25.Pei, S., Jorgensen, J.D., Dabrowski, B., Hinks, D.G., Richards, D.R., Mitchell, A.W., Newsam, J.M., Sinha, S.K., Vaknin, D., Jacobson, A.J., Phys. Rev. B 41, 4126 (1990).CrossRefGoogle Scholar
26.Woodward, P.M., Acta Crystallogr., Sect. B: Struct. Sci. 53, 32 (1997).CrossRefGoogle Scholar
27.Woodward, P.M., Acta Crystallogr., Sect. B: Struct. Sci. 53, 44 (1997).CrossRefGoogle Scholar
28.Goldschmidt, V.M., Naturwissenschaften 14, 477 (1926).CrossRefGoogle Scholar
29.Tomioka, Y., Tokura, Y., Phys. Rev. B 70, 014432 (2004).CrossRefGoogle Scholar
30.Torrance, J.B., Lacorre, P., Nazzal, A.I., Ansaldo, E.J., Niedermayer, C., Phys. Rev. B 45, 8209 (1992).CrossRefGoogle Scholar
31.Thomas, N.W., Acta Crystallogr., Sect. B: Struct. Sci. 52, 16 (1996).CrossRefGoogle Scholar
32.Angel, R.J., Zhao, J., Ross, N.L., Phys. Rev. Lett. 95, 025503 (2005).CrossRefGoogle Scholar
33.Tohei, T., Kuwabara, A., Yamamoto, T., Oba, F., Tanaka, I., Phys. Rev. Lett. 94, 035502 (2005).CrossRefGoogle Scholar
34.Zhou, J.-S., Goodenough, J.B., Phys. Rev. B 68, 144406 (2003).CrossRefGoogle Scholar
35.Dabrowski, B., Kolesnik, S., Baszczuk, A., Chmaissem, O., Maxwell, T., Mais, J., J. Solid State Chem. 178, 629 (2005).CrossRefGoogle Scholar
36.Zhou, J.S., Goodenough, J.B., Dabrowski, B., Klamut, P.W., Bukowski, Z., Phys. Rev. Lett. 84, 526 (2000).CrossRefGoogle Scholar
37.Medarde, M.L., J. Phys. Condens. Matter 9, 1679 (1997).CrossRefGoogle Scholar
38.Xie, C.K., Budnick, J.I., Hines, W.A., Wells, B.O., Woicik, J.C., Appl. Phys. Lett. 93, 182507 (2008).CrossRefGoogle Scholar
39.May, S.J., Kim, J.W., Rondinelli, J.M., Karapetrova, E., Spaldin, N.A., Bhattacharya, A., Ryan, P.J., Phys. Rev. B 82, 014110 (2010).CrossRefGoogle Scholar
40.He, F., Wells, B.O., Shapiro, S.M., Phys. Rev. Lett. 94, 176101 (2005).CrossRefGoogle Scholar
41.Jia, C.L., Mi, S.B., Faley, M., Poppe, U., Schubert, J., Urban, K., Phys. Rev. B 79, 081405R (2009).CrossRefGoogle Scholar
42.Vailionis, A., Boschker, H., Siemons, W., Houwman, E.P., Blank, D.H.A., Rijnders, G., Koster, G., Phys. Rev. B 83, 064101 (2011).CrossRefGoogle Scholar
43.Borisevich, A., Ovchinnikov, O.S., Chang, H.J., Oxley, M.P., Yu, P., Seidel, J., Eliseev, E.A., Morozovska, A.N., Ramesh, R., Pennycook, S.J., Kalinin, S.V., ACS Nano 4, 6071 (2010).CrossRefGoogle Scholar
44.Han, Y., Reaney, I.M., Johnson-Wilke, R.L., Telli, M.B., Tinberg, D.S., Levin, I., Fong, D.D., Fister, T.T., Streiffer, S.K., Trolier-McKinstry, S., J. Appl. Phys. 107, 123517 (2010).CrossRefGoogle Scholar
45.Miniotas, A., Vailionis, A., Svedberg, E.B., Karlsson, U.O., J. Appl. Phys. 89, 2134 (2001).CrossRefGoogle Scholar
46.Wakabayashi, Y., Journal of Physics: Condensed Matter 23, 483001 (2011).Google Scholar
47.Muller, D.A., Nat. Mater. 8, 263 (2009).CrossRefGoogle Scholar
48.Rondinelli, J.M., Spaldin, N.A., Adv. Mater. 23, 3363 (2011).CrossRefGoogle Scholar
49.Ramesh, R., Schlom, D.G., Mater. Res. Soc. Bull. 33, 1006 (2008).CrossRefGoogle Scholar
50.Streiffer, S.K., Fong, D.D., Mater. Res. Soc. Bull. 34, 832 (2009).CrossRefGoogle Scholar
51.Schlom, D.G., Chen, L.-Q., Eom, C.-B., Rabe, K.M., Streiffer, S.K., Triscone, J.M., Annu. Rev. Mater. Res. 37, 589 (2007).CrossRefGoogle Scholar
52.Thiele, C., Dorr, K., Bilani, O., Rodel, J., Schultz, L., Phys. Rev. B 75, 054408 (2007).CrossRefGoogle Scholar
53.Adamo, C., Ke, X., Wang, H.Q., Xin, H.L., Heeg, T., Hawley, M.E., Zander, W., Schubert, J., Schiffer, P., Muller, D.A., Maritato, L., Schlom, D.G., Appl. Phys. Lett. 95, 112504 (2009).CrossRefGoogle Scholar
54.Lee, J.H., Fang, L., Vlahos, E., Ke, X.L., Jung, Y.W., Kourkoutis, L.F., Kim, J.W., Ryan, P.J., Heeg, T., Roeckerath, M., Goian, V., Bernhagen, M., Uecker, R., Hammel, P.C., Rabe, K.M., Kamba, S., Schubert, J., Freeland, J.W., Muller, D.A., Fennie, C.J., Schiffer, P., Gopalan, V., Johnston-Halperin, E., Schlom, D.G., Nature 466, 954 (2010).CrossRefGoogle Scholar
55.Liu, J., Kareev, M., Gray, B., Kim, J.W., Ryan, P., Dabrowski, B., Freeland, J.W., Chakhalian, J., Appl. Phys. Lett. 96, 233110 (2010).CrossRefGoogle Scholar
56.Takamura, Y., Chopdekar, R.V., Arenholz, E., Suzuki, Y., Appl. Phys. Lett. 92, 162504 (2008).CrossRefGoogle Scholar
57.Wong, F.J., Baek, S.H., Chopdekar, R.V., Mehta, V.V., Jang, H.W., Eom, C.B., Suzuki, Y., Phys. Rev. B 81, 161101(R) (2010).CrossRefGoogle Scholar
58.Okuyama, D., Nakamura, M., Wakabayashi, Y., Itoh, H., Kumai, R., Yamada, H., Taguchi, Y., Arima, T., Kawasaki, M., Tokura, Y., Appl. Phys. Lett. 95, 152502 (2009).CrossRefGoogle Scholar
59.Suzuki, Y., Hwang, H.Y., Cheong, S.W., van Dover, R.B., Appl. Phys. Lett. 71, 140 (1997).CrossRefGoogle Scholar
60.Boschker, H., Mathews, M., Houwman, E.P., Nishikawa, H., Vailionis, A., Koster, G., Rijnders, G., Blank, D.H.A., Phys. Rev. B 79, 214425 (2009).CrossRefGoogle Scholar
61.Hohenberg, P., Kohn, W., Phys. Rev. 136, B864 (1964).CrossRefGoogle Scholar
62.Kohn, W., Sham, L.J., Phys. Rev. 140, A1133 (1965).CrossRefGoogle Scholar
63.Hatt, A.J., Spaldin, N.A., Phys. Rev. B 82, 195402 (2010).CrossRefGoogle Scholar
64.Son, J., Moetakef, P., LeBeau, J.M., Ouellette, D., Balents, L., Allen, S.J., Stemmer, S., Appl. Phys. Lett. 96, 062114 (2010).CrossRefGoogle Scholar
65.Chakhalian, J., Rondinelli, J.M., Liu, J., Gray, B.A., Kareev, M., Moon, E.J., Prasai, N., Cohn, J. L., Varela, M., Tung, I.C., Bedzyk, M.J., Altendorf, S.G., Strigari, F., Dabrowski, B., Tjeng, L.H., Ryan, P.J., Freeland, J.W., Phys. Rev. Lett. 107, 116805 (2011).CrossRefGoogle Scholar
66.Glazer, A.M., Acta Crystallogr., Sect. A: Found. Crystallogr. 31, 756 (1975).CrossRefGoogle Scholar
67.Woicik, J.C., Xie, C.K., Wells, B.O., J. Appl. Phys. 109, 083519 (2011).CrossRefGoogle Scholar
68.Rondinelli, J.M., Coh, S., Phys. Rev. Lett. 106, 235502 (2011).CrossRefGoogle Scholar
69.Scott, J.F., Adv. Mater. 22, 2106 (2010).CrossRefGoogle Scholar
70.Zeches, R.J., Rossell, M.D., Zhang, J.X., Hatt, A.J., He, Q., Yang, C.H., Kumar, A., Wang, C.H., Melville, A., Adamo, C., Sheng, G., Chu, Y.H., Ihlefeld, J.F., Erni, R., Ederer, C., Gopalan, V., Chen, L.Q., Schlom, D.G., Spaldin, N.A., Martin, L.W., Ramesh, R., Science 326, 977 (2009).CrossRefGoogle Scholar
71.Bea, H., Ziegler, B., Bibes, M., Barthelemy, A., Parush, P., J. Phys. Condens. Matter 23, 142201 (2011).CrossRefGoogle Scholar
72.Malashevich, A., Vanderbilt, D., Phys. Rev. B 80, 224407 (2009).CrossRefGoogle Scholar
73.Lee, J.H., Rabe, K.M., Phys. Rev. Lett. 104, 207204 (2010).CrossRefGoogle Scholar
74.Bhattacharjee, S., Bousquet, E., Ghosez, P., Phys. Rev. Lett. 102, 117602 (2009).CrossRefGoogle Scholar
75.Eklund, C.J., Fennie, C.J., Rabe, K.M., Phys. Rev. B 79, 220101(R) (2009).CrossRefGoogle Scholar
76.Zayak, A.T., Huang, X., Neaton, J.B., Rabe, K.M., Phys. Rev. B 74, 094104 (2006).CrossRefGoogle Scholar
77.Zayak, A.T., Huang, X., Neaton, J.B., Rabe, K.M., Phys. Rev. B 77, 214410 (2008).CrossRefGoogle Scholar
78.Borisevich, A.Y., Chang, H.J., Huijben, M., Oxley, M.P., Okamoto, S., Niranjan, M.K., Burton, J.D., Tsymbal, E.Y., Chu, Y.H., Yu, P., Ramesh, R., Kalinin, S.V., Pennycook, S.J., Phys. Rev. Lett. 105, 087204 (2010).CrossRefGoogle Scholar
79.Rondinelli, J.M., Spaldin, N.A., Phys. Rev. B 82, 113402 (2010).CrossRefGoogle Scholar
80.He, J., Borisevich, A., Kalinin, S.V., Pennycook, S.J., Pantelides, S.T., Phys. Rev. Lett. 105, 227203 (2010).CrossRefGoogle Scholar
81.Vlasko-Vlasov, V.K., Lin, Y.K., Miller, D.J., Welp, U., Crabtree, G.W., Nikitenko, V.I., Phys. Rev. Lett. 84, 2239 (2000).CrossRefGoogle Scholar
82.Proffit, D.L., Jang, H.W., Lee, S., Nelson, C.T., Pan, X.Q., Rzchowski, M.S., Eom, C.B., Appl. Phys. Lett. 93, 111912 (2008).CrossRefGoogle Scholar
83.Chang, S.H., Chang, Y.J., Jang, S.Y., Jeong, D.W., Jung, C.U., Kim, Y.-J., Chung, J.-S., Noh, T.W., Phys. Rev. B 84, 104101 (2011).CrossRefGoogle Scholar
84.Segal, Y., Garrity, K.F., Vaz, C.A.F., Hoffman, J.D., Walker, F.J., Ismail-Beigi, S., Ahn, C.H., Phys. Rev. Lett. 107, 105501 (2011).CrossRefGoogle Scholar
85.Hoppler, J., Stahn, J., Bouyanfif, H., Malik, V.K., Patterson, B.D., Willmott, P.R., Cristiani, G., Habermeier, H.U., Bernhard, C., Phys. Rev. B 78, 134111 (2008).CrossRefGoogle Scholar
86.May, S.J., Smith, C.R., Kim, J.-W., Karapetrova, E., Bhattacharya, A., Ryan, P.J., Phys. Rev. B 83, 153411 (2011).CrossRefGoogle Scholar
87.Rondinelli, J.M., Spaldin, N.A., Phys. Rev. B 81, 085109 (2010).CrossRefGoogle Scholar
88.Blanca-Romero, A., Pentcheva, R., Phys. Rev. B 84, 195450 (2011).CrossRefGoogle Scholar
89.Benedek, N.A., Fennie, C.J., Phys. Rev. Lett. 106, 107204 (2011).CrossRefGoogle Scholar
90.Dingle, R., Stormer, H.L., Gossard, A.C., Wiegmann, W., Appl. Phys. Lett. 33, 665 (1978).CrossRefGoogle Scholar
91.Kozuka, Y., Kim, M., Ohta, H., Hikita, Y., Bell, C., Hwang, H.Y., Appl. Phys. Lett. 97, 222115 (2010).CrossRefGoogle Scholar
92.Santos, T.S., Kirby, B.J., Kumar, S., May, S.J., Borchers, J.A., Maranville, B.B., Zarestky, J., te Velthuis, S.G.E., van der Brink, J., Bhattacharya, A., Phys. Rev. Lett. 107, 167202 (2011).CrossRefGoogle Scholar
93.Jalan, B., Stemmer, S., Mack, S., Allen, S.J., Phys. Rev. B 82, 081103(R) (2010).CrossRefGoogle Scholar
94.Jang, H.W., Felker, D.A., Bark, C.W., Wang, Y., Niranjan, M.K., Nelson, C.T., Zhang, Y., Su, D., Folkman, C.M., Baek, S.H., Lee, S., Janicka, K., Zhu, Y., Pan, X.Q., Fong, D.D., Tsymbal, E.Y., Rzchowski, M.S., Eom, C.B., Science 331, 886 (2011).CrossRefGoogle Scholar
95.Garcia-Fernandez, P., Aramburu, J.A., Barriuso, M.T., Moreno, M., J. Phys. Chem. Lett. 1, 647 (2010).CrossRefGoogle Scholar
96.Mannhart, J., Schlom, D.G., Science 327, 1607 (2010).CrossRefGoogle Scholar
97.Stroppa, A., Fukushima, T., Picozzi, S., Perez-Mato, J.M., Phys. Chem. Chem. Phys. 13, 12186 (2011).Google Scholar
98.Lopez-Perez, J., Iniguez, J., Phys. Rev. B 84, 075121 (2011).CrossRefGoogle Scholar
99.Rondinelli, J.M., Fennie, C.J., arXiv:1106.0049 (2011), in pressAdvanced Materials (2012).Google Scholar
100.Gopalan, V., Litvin, D.B., Nat. Mater. 10, 376 (2011).CrossRefGoogle Scholar
101.Rata, A.D., Herklotz, A., Nenkov, K., Schultz, L., Dorr, K., Phys. Rev. Lett. 100, 076401 (2008).CrossRefGoogle Scholar
102.Korff Schmising, C. v., Harpoeth, A., Zhavoronkov, N., Ansari, Z., Aku-Leh, C., Woerner, M., Elsaesser, T., Bargheer, M., Schmidbauer, M., Vrejoiu, I., Hesse, D., Alexe, M., Phys. Rev. B 78, 060404(R) (2008).CrossRefGoogle Scholar
103.Rini, M., Tobey, R., Dean, N., Itatani, J., Tomioka, Y., Tokura, Y., Schoenlein, R.W., Cavalleri, A., Nature 449, 72 (2007).CrossRefGoogle Scholar
104.Fausti, D., Tobey, R.I., Dean, N., Kaiser, S., Dienst, A., Hoffmann, M.C., Pyon, S., Takayama, T., Takagi, H., Cavalleri, A., Science 331, 189 (2011).CrossRefGoogle Scholar

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