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Journal of Crystal Growth 267 (2004) 548–553

Epitaxial and oriented YMnO3 film growth by pulsed laser deposition
J. Dho, C.W. Leung, J.L. MacManus-Driscoll, M.G. Blamire*
Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ, UK Received 16 January 2004; accepted 7 April 2004

Communicated by D.T.J. Hurle

Abstract We have studied the crystal growth behavior of multiferroic YMnO3 films synthesized by pulsed laser deposition on several different substrates. The growth orientation and surface morphology of YMnO3 films were sensitively dependent on the substrates and deposition conditions. An excellent epitaxial hexagonal YMnO3 film was grown on the (1 1 1) Y-stabilized ZrO2 substrate, but with increasing the oxygen pressure few percentage of 30 twin growth was developed. On the other hand, the YMnO3 film on the Si substrate with an amorphous SiO2 layer exhibited (0 0 0 1) or ð1 1 2 1Þ orientation. The (0 0 0 1) oriented hexagonal YMnO3 phase was a stable one under tensile stress by the (0 0 0 1) % Al2O3 substrate, while it competed with the (0 1 1)-oriented orthorhombic YMnO3 phase under the compressive stress by the (1 1 1) SrTiO3 substrate. r 2004 Elsevier B.V. All rights reserved.
PACS: 77.55; 61.10.N; 61.16.C Keywords: A1. X-ray diffraction; A3. Laser epitaxy; B1. Oxides; B2. Dielectric materials

1. Introduction The hexagonal manganite YMnO3 is one of the representative multiferroic materials which exhibit simultaneously ferroelectricity and magnetism [1,2]. Upon cooling, the YMnO3 undergoes a paraelectric–ferroelectric transition at the Curie
*Corresponding author. Tel.: +44-1223-334374; fax: +441223-334373. E-mail address: mb52@cam.ac.uk (M.G. Blamire).

temperature TC B900 K, and it displays an antiferromagnetic transition at around 70 K [3]. For last few years, the YMnO3 thin film has attracted interest as a candidate for application to the nonvolatile ferroelectric random access memory because YMnO3 has good retention property [4–7]. YMnO3 films have been synthesized by various techniques such as molecular beam epitaxy (MBE) [5,6], pulsed laser deposition (PLD) [7–12], sputtering [13–15], and chemical solution routes [16–22]. Imada et al. [5] and Ito et al. [7] reported

0022-0248/$ - see front matter r 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jcrysgro.2004.04.028

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that YMnO3 films synthesized by MBE and PLD on (1 1 1)Pt/(0 0 0 1)Al2O3 and (1 1 1)Y2O3/(1 1 1)Si grew epitaxially and displayed the full width half maximum (FWHM) of about 0.7 in X-ray diffraction rocking curve. However, most films displayed a polycrystalline property with a random orientation, but some films deposited with post-annealing showed c-axis texture [13,14,19]. The degree of crystallinity of the YMnO3 film depends on many kinds of parameters when it grows on a substrate. In order to make an YMnO3 film with good potential application, the control of the crystal orientation is very important because the ferroelectric polarization of the YMnO3 appears along to the c-axis [2,3]. In this paper, we have investigated the characteristics of the film growth with the substrate giving tensile or compressive stress to the YMnO3 layer. The crystallinity and the surface morphology of the YMnO3 film were clearly dependent on the lattice matching between the substrate and the YMnO3. We also studied the crystallinity of the YMnO3 film with the oxygen pressure, and found that the epitaxial growth of the YMnO3 film on the Y-stabilized ZrO2 substrate is gradually disturbed by the increase of the oxygen pressure. In addition, the YMnO3 film on the Si substrate displayed (0 0 0 1) or ð1 1 2 1Þ orientation. % 2. Experimental details Thin films of hexagonal YMnO3 have been grown on (1 1 1) Y-stabilized ZrO2 (YSZ), (1 1 1) Si, (0001) Al2O3 (ALO), and (1 1 1) SrTiO3 (STO) substrates by pulsed laser deposition. The hexagonal in-plane lattice parameters of substrates and bulk YMnO3 are summarized in Table 1. The

hexagonal single phase YMnO3 target was prepared by a solid state reaction method using a stoichiometric Y2O3 and Mn2O3 mixture [23]. The substrates were cleaned with high-purity acetone and ethanol for 5 min in ultrasonic cleaner, respectively. After then, the substrates were blown with nitrogen gas. The deposition conditions were as follows: substrate temperature of 800–850 C, Oxygen pressure of 0.1–50 m Torr, wave length of KrF excimer laser of 248 nm, the laser pulse rate of 2–5 Hz. After deposition, in situ annealing to improve the oxygen stoichiometry was performed in an oxygen pressure of 100 m Torr for 10 min at the same temperature. The thickness of the films, controlled by the number of pulses, ranged from 6 to 250 nm. The structural properties of YMnO3 thin films were characterized using X-ray diffraction (XRD), and the surface morphologies of films were observed by atomic force microscopy (AFM).

3. Results and discussion Fig. 1 shows the XRD pattern of the YMnO3 films grown on the (1 1 1) YSZ substrate. We can see only strong (0001) peaks of YMnO3, except for the YSZ substrate peak, which suggests that the YMnO3 film grows epitaxially because it has

Table 1 The in-plane hexagonal lattice parameters Materials (1 1 1) YSZ (0 0 0 1) ALO YmnO3 Lattice ( constant (A) 3.631 4.758 3.533 Materials (1 1 1) Si (1 1 1) STO at P63/mmc Lattice ( constant (A) 3.840 2.758 Fig. 1. X-ray diffraction patterns of YMnO3 films grown on the (1 1 1) YSZ substrate with the film thickness. The XRD data also includes Ka and Kb lines of the (1 1 1) YSZ peak. The inset displays the lattice constant c with the film thickness.

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a good lattice matching with the substrate. The lattice mismatch between the bulk YMnO3 material and the YSZ substrate is about 2.8%. The inset displays the c-axis lattice constant with the film thickness. The lattice constant c was estimated from the position of the (0 0 0 6) peak. The lattice constant c gradually decreases with increasing the film thickness and approaches to the lattice constant of the bulk material [3]. As seen in Table 1, the in-plane lattice constant of YMnO3 is smaller than that of the YSZ substrate, so the YMnO3 layer on the YSZ substrate is under inplane tensile stress. The larger c value of the thin film in comparison with the bulk material is surprising because the in-plane tensile stress generally induces the contraction of the out-ofplane lattice parameter of epitaxial films. This anomalous behavior may be related to a 2D-like characteristic of the hexagonal structure YMnO3. We conjecture that the in-plane lattice expansion by the tensile stress likely causes the weakening of inter-plane ionic bond strength in the YMnO3 layer as well as that of intra-plane ionic bond strength. Fig. 2 shows the variation of X-ray rocking curves of the YMnO3 (0 0 0 4) peak with deposition oxygen pressure. The FWHM is only about 0.06 , indicating the YMnO3 film has an excellent crystalline quality. The FWHM value is almost independent of the oxygen pressure. In order to

investigate the in-plane texture of the films, we measured the X-ray f-scan of the ð1 1 2 2Þ YMnO3 % peak as seen in Fig. 3. For deposition oxygen pressure below 1 m Torr, the f-scan data shows a 6-fold symmetry, implying hexagonal epitaxial films. Above 10 m Torr, however, the YMnO3 film shows an additional small peaks with 30 offset, indicates that there is 30 twin growth. The relative intensity of small peaks to main peaks is about 1–3%. The composition analysis by the electron diffraction X-ray (EDX) suggested that the Y and Mn atomic percentage changed by about 2% with the oxygen pressure. The 30 twin growth may be closely related to such a subtle composition change. Fig. 4 displays the XRD data of YMnO3 films on the (0 0 0 1) ALO substrate with the oxygen pressure. It shows only (0 0 0 1) peaks, but the intensities of each peak are much smaller than those on the YSZ substrate. The FWHM of the XRD rocking curve is about 2–3 , as seen in the inset of Fig. 4. This means that the YMnO3 film on the ALO substrate is a highly textured c-axisoriented film rather than a fully epitaxial one because of the large lattice mismatching between the YMnO3 and the ALO substrate. It is worthy to talk that the c-axis oriented growth on the ALO substrate was independent of the oxygen background pressure. On the other hand, the growth orientation of YMnO3 film on Si substrate with an

Fig. 2. The rocking curves of the (0 0 0 4) YMnO3 peak with deposition oxygen pressure. The inset displays the full width half maximum (FWHM) of the (0 0 0 4) peaks.

Fig. 3. The f-scans of the ð1 1 2 2Þ YMnO3 peak with % deposition oxygen pressure.

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Fig. 4. X-ray diffraction patterns of YMnO3 films grown on the (0 0 0 1) ALO substrate. The inset displays the rocking curves of the (0 0 0 4) YMnO3 peak.

peaks. This means that the (0 0 0 1) or ð1 1 2 1Þ oriented growth of the YMnO3 film on the% Si substrate is dependent on the oxygen pressure when all other parameters are fixed. The surface morphology of the YMnO3 film depends on various parameters such as the substrate and the oxygen pressure. Fig. 6 displays the surface morphology of YMnO3 films measured at 10 and 0.1 m Torr. The average roughness on ( the YSZ substrate was 0.9 and 1.0 A for 10 and 0.1 m Torr, respectively. In the case of epitaxial films, the surface roughness seems to be independent of the oxygen pressure. On the other hand, the highly oriented films exhibited an obvious dependence on the oxygen pressure. The average ( roughness on the ALO substrate was 1.9 and 3.9 A for 10 and 0.1 m Torr, respectively. In addition, the surface roughness displayed a clear difference with the growth orientation of the YMnO3 film. On the Si substrate, the average roughness of the YMnO3

Fig. 5. X-ray diffraction patterns of YMnO3 films grown on the (1 1 1) Si substrate with SiO2 layer.

amorphous SiO2 layer is sensitively dependent on the oxygen pressure, as seen in Fig. 5. At 10 m Torr, the (0 0 0 1) peak of the YMnO3 films is strongly observed, but it is drastically suppressed with decreasing the oxygen pressure. The strongest XRD peak at 0.1 m Torr is ð1 1 2 1Þ %

Fig. 6. Surface morphology of YMnO3 films grown on the (1 1 1) YSZ, the (0 0 0 1)ALO, and the (1 1 1) Si substrate at 10 and 0.1 m Torr. The scan size is 5 mm  5 mm, and the contrast depth of images is 20 nm.

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film with (0 0 0 1) orientation at 10 m Torr was ( 2.4 A, while with ð1 1 2 1Þ orientation at 0.1 m Torr % ( was only 1.1 A. Furthermore, the surface roughness is dependent on the crystallinity of film as well. If we compare the roughness of three YMnO3 films with (0 0 0 1) orientation at 10 m Torr on different substrates, we can find the better the crystallinity is, the smaller the roughness is. In order to investigate the crystal growth behavior of YMnO3 under compressive stress, we made an YMnO3 film on the (1 1 1) STO substrate with a smaller in-plane lattice parameter, as seen in Table 1. Fig. 7 is the XRD profile of the YMnO3 film on the (1 1 1) STO, which shows orthorhombic (0 1 1) peaks as well as hexagonal (0 0 0 1) peaks. Iliev et al. [24] reported that the orthorhombic phase in the bulk material appeared when the YMnO3 was sintered in a high-pressure furnace. Accordingly, we conjecture that the STO substrate gives a strong compressive pressure to the YMnO3 layer; thus it partially induces an orthorhombic phase. It is known that the hexagonal YMnO3 phase is ferroelectric, but the orthorhombic phase is not ferroelectric. This indicates that the compressive strain of the YMnO3 layer should be fully relaxed to make one with a good ferroelectric property.

4. Conclusion Epitaxial and highly oriented YMnO3 thin films have been synthesized on several different substrates. The crystallinity and surface morphology of YMnO3 thin films were dependent on the lattice mismatching and the oxygen background pressure. On the (1 1 1) YSZ substrate, a very good epitaxial YMnO3 film was obtained below 1 m Torr, but a 30 twin growth was partly observed above 10 m Torr. The YMnO3 film on the (0 0 0 1) ALO substrate grew with the c-axis orientation, which is independent of the oxygen pressure. On the other hand, the (0 0 0 1) or ð1 1 2 1Þ oriented film on the % Si substrate with SiO2 layer was obtained with the oxygen pressure. In the case of the (1 1 1) SrTiO3 substrate, the orthorhombic YMnO3 phase competing with the hexagonal phase was induced by the strong compressive stress. We expect that our systematic study will be a guide to make a highquality YMnO3 film, which can be utilized in various ferroelectric and multiferroic applications.

Acknowledgements The authors would like to thank M. Vickers for X-ray diffraction measurement. This was supported by the Post-doctoral Fellowship Program of Korea Science & Engineering Foundation (KOSEF) and by the Engineering and Physical Sciences Research Council (EPSRC).

References
[1] N.A. Hill, J. Phys. Chem. B 104 (2000) 6694. [2] M. Fibig, T. Lottermoser, D. Frohlich, A.V. Goltsev, R.V. Pisarev, Nature 419 (2002) 818. [3] B.B. van Aken, A. Meetsma, T.T.M. Palstra, Acta Crystallogr. C 57 (2001) 230. [4] N. Fujimura, T. Ishida, T. Yoshimura, T. Ito, Appl. Phys. Lett. 69 (1996) 1011. [5] S. Imada, T. Kuraoka, E. Tokumitsu, H. Ishiwara, Jpn. J. Appl. Phys. 40 (2001) 666. [6] S. Imada, S. Shouriki, E. Tokumitsu, H. Ishiwara, Jpn. J. Appl. Phys. 37 (1998) 6497. [7] D. Ito, N. Fujimura, T. Yoshimura, T. Ito, J. Appl. Phys. 94 (2003) 4036;

Fig. 7. X-ray diffraction pattern of YMnO3 film grown on (1 1 1) STO substrate. The hexagonal phase is marked by H, and the orthorhombic phase is marked by O.

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J. Dho et al. / Journal of Crystal Growth 267 (2004) 548–553 D. Ito, N. Fujimura, T. Yoshimura, T. Ito, J. Appl. Phys. 93 (2003) 5563. D. Ito, N. Fujimura, T. Ito, Jpn. J. Appl. Phys. 39 (2000) 5525. N. Fujimura, H. Sakata, D. Ito, T. Yoshimura, T. Yokota, T. Ito, J. Appl. Phys. 93 (2003) 6990. E. Rokuta, Y. Hotta, H. Tabata, H. Kobayashi, T. Kawai, J. Appl. Phys. 88 (2000) 6598. N. Fujimura, S. Azuma, N. Aoki, T. Yoshimura, J. Appl. Phys. 94 (2003) 4036. T. Yoshimura, N. Fujimura, T. Ito, Appl. Phys. Lett. 73 (1998) 414. T. Yoshimura, N. Fujimura, D. Ito, T. Ito, J. Appl. Phys. 80 (1996) 7084. Y.T. Kim, I.S. Kim, S.I. Kim, D.C. Yoo, J.Y. Lee, J. Appl. Phys. 94 (2003) 4859. H.N. Lee, Y.T. Kim, Y.K. Park, Appl. Phys. Lett. 74 (1999) 3887. K. Suzuki, K. Nishizawa, T. Miki, K. Kato, J. Crystal Growth 237 (2002) 482. 553

[8] [9] [10] [11] [12] [13] [14] [15] [16]

[17] W.-C. Shin, J.-H. Yang, K.-J. Choi, Y.-A. Jeon, J. Vac. Sci. Technol. B 19 (2001) 239. [18] K.-J. Choi, W.-C. Shin, J.-W. Yang, S.-G. Yoon, Appl. Phys. Lett. 75 (1999) 722. [19] W.-C. Yi, C.-S. Seo, S.-I Kwun, J.-G. Yoon, Appl. Phys. Lett. 77 (2000) 1044. [20] H. Kitahata, K. Tadanaga, T. Minami, N. Fujimura, T. Ito, Appl. Phys. Lett. 75 (1999) 719. [21] H. Kitahata, K. Tadanaga, T. Minami, N. Fujimura, T. Ito, Jpn. J. Appl. Phys. 38 (1999) 5448. [22] N. Fujimura, H. Tanaka, H. Kitahata, K. Tadanaga, T. Yoshimura, T. Ito, T. Minami, Jpn. J. Appl. Phys. 36 (1997) L1601. [23] J. Dho, W.S. Kim, N.H. Hur, Phys. Rev. Lett. 89 (2002) 027202. [24] M.N. Iliev, M.V. Abrashev, H.-G. lee, V.N. Popov, Y.Y. Sun, C. Thomsen, R.L. Meng, C.W. Chu, Phys. Rev. B 57 (1998) 2872.