Thin Solid Films 429 (2003) 282285

An interfacial defect layer observed at (Ba,Sr)TiO3 yPt interface

H.Z. Jina, J. Zhua,*, P. Ehrhartb, F. Fitsilisb, C.L. Jiab, S. Regneryb, K. Urbanb, R. Waserb
a

Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, PR China b Institut fur Festkorperforschung, Forschungszentrum Julich GmbH, D-52425 Julich, Germany

Received 14 December 2002; received in revised form 14 December 2002; accepted 18 December 2002

Abstract Barium strontium titanate (Ba,Sr)TiO3 (BST) thin-films on Pt-substrates were studied by transmission electron microscopy. The films show a columnar structure with the grains of 1050 nm in diameter. These are oriented parallel to the w0 0 1x direction which in turn is parallel to the film growth direction. No amorphous intergrain regions occur. The high-resolution lattice fringe pictures show for the first time that over horizontally extended areas of the interface the lattice of the BST film is modified by the introduction of a defect layer. This observation is discussed in terms of a structural origin of the so-called dead-layer effect responsible for a reduction of the film permittivity with decreasing foil thickness. 2003 Elsevier Science B.V. All rights reserved.
Keywords: Transmission electron microscopy; Interfacial defect layer; Barium strontium titanate; High-density storage

1. Introduction The Perovskite barium strontium titanate (Ba,Sr)TiO3 (BST), due to its high dielectric constant, is a leading candidate for dielectric to be used in future dynamic random-access memories w1x. However, it has been found that with respect to the electrical properties BST in the form of thin-films does by far not reach the qualities of bulk material w2x. In particular, the dielectric constant of films decreases when the film thickness is reduced w1,3,4x. A similar size dependence of thin-film permittivity was observed in ferroelectric Pb(Zr,Ti)O3 films on platinum electrode w5x. A variety of mechanisms have been discussed which could explain the observed deterioration of the materials properties w2,4x. Most frequently the so-called deadlayer model is employed w16x. The basic assumption of this model is that during film deposition an intermediate layer of low dielectric constant is formed between the BST film and the electrodes. The interfacial layer, acting as an additional capacitor connected in series with the bulk of the film, accounts for the observed low permittivity of the whole stack. Although in this basis a
*Corresponding author. Tel.: q86-106-2794026; fax: q86-1062772507. E-mail address: jzhu@mail.tsinghua.edu.cn (J. Zhu). 0040-6090/03/$ - see front matter PII: S 0 0 4 0 - 6 0 9 0 0 2 . 0 1 3 3 0 - 5

quantitative description of the size effect can be achieved, the validity of the dead-layer model remains a point of controversy, last not least since the intermediate layer has so far not been identified experimentally w1,5,7x. In the present work the interfacial area of BST films on Pt-electrode was studied by transmission electron microscopy (TEM). The high-resolution lattice fringe pictures show for the first time that over horizontally extended areas of the interface the lattice of the BST film is modified by the introduction of a defect layer. 2. Experimental details The BST thin-films investigated in our study were deposited by metal-organic chemical vapor deposition onto a PtyTiO2 ySiO2 ySi substrate at a substrate temperature of 650 8C. The composition of the films is around (Ba0.7,Sr0.3)TiO3. By varying the deposition time, BST films with various thicknesses are obtained. Details of the growth procedure have been published elsewhere w8 x . Both plan-view and cross-sectional specimens were used for our structure investigations. Cross-sectional samples were prepared by cutting the film-covered wafer into slices. Two of these slices were glued face-to-face

2003 Elsevier Science B.V. All rights reserved.

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straight and usually run through the whole film thickness from the BSTyPt interface to the surface of the film. The morphology of the BST film was also studied under plan-view conditions. Fig. 2a shows that the grain diameter is approximately 1050 nm. The orientation distribution of the grains was studied by selected-area electron diffraction. The results (Fig. 2a inset) again indicate that w0 0 1x direction of the grains is parallel to the substrate normal. This is corroborated by the highresolution lattice fringe picture of Fig. 2b. The essentially uniform lattice contrast indicates a remarkably high degree of parallel orientation of the individual grains, within a few tenths of a degree. No amorphous intergrain regions can be detected, even in the triplejunctions. This is in contrary to the observation made

Fig. 1. (a) A low-magnification overview of a cross-sectional specimen, showing the BSTyPtyTiO2ySiO2 layered structure on a Si substrate. Film thickness is approximately 80 nm. (b) TEM image at a higher magnification showing the columnar grain structure. Film thickness is approximately 22 nm.

forming a sandwiched structure with the BSTyPt interface in edge-on orientation. Following the conventional way of sample preparation, i.e. by mechanical grinding and dimpling perpendicular to the sandwich plane, the specimens were finally thinned to perforation by ion milling. Plan-view samples were prepared by polishing and ion milling the wafer from the substrate side only. The high-resolution investigations were carried out in a JEOL 4000EX electron microscope operated at 400 kV. 3. Results Fig. 1a shows a low magnification overview of a cross-sectional specimen. The whole layer sequence from the Si-substrate to the top of the BST film can be seen. Both the BSTyPt interface and the surface of the BST layer are very flat over large areas. As a result, the thickness of the BST film is highly uniform, which is a pre-requisite for the achievement of bit-to-bit uniformity in highly integrated devices. As shown in the highmagnification picture of Fig. 1b the BST film shows a columnar structure with the grains preferentially oriented parallel to the w0 0 1x direction which in turn is parallel to the film growth direction. The grain boundaries are

Fig. 2. (a) Plan-view TEM image of the BST film. The film has a strong (0 0 1) fiber texture, revealed by selected-area electron diffraction patterns (inset). (b) Plan-view high-resolution TEM lattice image showing three grains of the BST film. The grain boundaries are well crystallized and no amorphous region is observed.

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Fig. 3. High-resolution TEM lattice image of the BSTyPt interface. The results show that our films are crystalline, with no amorphous phase present at the BSTyPt interface. However, as indicated by the white lines, the separation of the two bb lines near the interface is larger than the separation of the rows more far away from the interface.

in Ti-excess BST thin-films where amorphous Ti-rich regions are present at grain boundaries w7x. In our studies at very high-resolution we found that over horizontally extended areas the BST lattice is severely distorted close to the Pt substrate. An example of this is shown in the high-magnification lattice fringe picture taken along a w1 1 0x direction is shown in Fig. 3. Our contrast calculations showed that the BaO columns are imaged dark on a bright background. Approaching the BSTyPt interface from the top we see an alternating sequence of a very bright horizontal row of dots (denoted by bb in the figure) and of a less bright row (b). Following this bbbbbb-sequence into the interface we find that the separation of the last two bb-type rows at the interface is larger than the separation of the rows more far away from the interface. The vertical distance of the horizontal white lines is 0.39 nm in good agreement with the lattice parameter of BST. The separation of the two lines marking the bbtype rows next to the interface is 0.48 nm, i.e. 22% larger. We note that taking pictures under different imaging conditions does change the contrast but leaves the fact of the described lattice irregularity at the interface unaffected. 4. Discussion As described above BST thin-films show a thickness dependent permittivity, i.e. the dielectric constant decreases with decreasing film thickness. As we could show by measurements of the dielectric properties, this does also hold true for the BST films investigated in our study w9x. Our present work shows that our films are crystalline, with no amorphous phase present at the BSTyPt interface or BST grain boundaries. Therefore, the possibility that an amorphous layer is the main factor that caused the size dependent permittivity can be ruled

out. However, our study for the first time provides evidence for a modification of the BST lattice at the interface with the Pt electrode. There, with respect to the bright bb-type lines, the lattice line separation is substantially increased. It is too early to assign any atomic positions to the high-resolution lattice fringe pictures. The resolution of the JEOL 4000EX is not sufficient to resolve the TiO or the O atomic columns which together with the BaO columns occur in the w1 1 0x projection of the BST structure. In addition spherical-aberration induced contrast delocalization represents a principle obstacle for a determination of the exact atomic occupation of the first atomic layer of BST in contact to the Pt substrate. We can describe the structure modification in terms of a planar fault extending along the (1 1 0) lattice plane. A candidate structure for an explanation of our observations is provided by RuddlesdenPopper (RP) planar fault w10x. In recent years a large number of Perovskitebased heterostructures have been studied. It was found that heteroepitaxial misfit strain, local excess alkalineearth element and oxygen deficiency is frequently accommodated in the thin-film systems by the formation of such faults w11,12x. Due to a local deviation in stoichiometry the bulk RP phases and related planar faults give rise to substantial changes of the dielectric properties making this type of defect layer a candidate for the explanation for the reduction of the dielectric constant close to the BSTyPt interface w13x. Acknowledgments This work is supported in part by the National Natural Sciences Foundation of China. References
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