journal

J. Ain. Ceramin. Soc., 86 [1] 149-51 (2003)

Two-Layer Crystallization of Amorphous YMnO 3 Thin Films on Si (100) Substrates
Dong Chul Yoo and Jeong Yong Lee
Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Korea

Ik Soo Kim and Yong Tae Kim
Semiconductor Materials Laboratory, Korea Institute of Science and Technology, Seoul 136-791. Korea During a rapid thermal annealing process at 850°C in a N2 ambient, an as-deposited amorphous YMInO3 thin film on Si (100) substrates was crystallized with two distinct layers. High-resolution transmission electron microscopy showed a top layer of c-axis-oriented YMnO3 and a bottom layer of polycrystalline YMnO_ in the 100-nm-thick YMnO3 thin film. The abrupt change of the crystalline orientation from the c-axis-preferred orientation to the random orientation is caused primarily by high stress induced by the c-axis-oriented YMnOQ, layer. High-resolution X-ray diffraction showed that the c-axis-oriented YMnO 3 /polycrystaliine YMnO3 structure effectively relieved the stress. I. Introduction evaluated using high-resolution X-ray diffraction (HRXRD). The relationship between stress and crystallization in the YMnO 3 thin films is discussed. H. Experimental Procedures YMnO 3 thin films were deposited on p-Si (100) substrates with radio frequency (rf) sputtering at room temperature using a YMnO_ single target (purity 99.9%) made by mixing Y2 03 and Mn2 03 powders at a ratio of 1:1. During the deposition in Ar + 02 ambient, the rf-power density and chamber pressure were fixed at 1.85 W/cm2 and 5 X l0-3 torr, respectively. The as-deposited 100-nm-thick YMnO_ films were crystallized by rapid thermal processing (RTP) in N atmosphere at 850°C for 3 min. The 2 microstructure of the YMnO 3 thin films was characterized by HRTEM (Model JEM-2000EX, JEOL, Tokyo, Japan) operating at 200 kV. To examine a stress in the YMnO3 /Si, Si (004) rocking curves were measured using HRXRD (Model RINT2000, Rigaku Co., Tokyo, Japan).

EcENTLY, ferroelectric thin films have attracted much attention Rfor use in nondestructive read out (NDRO) ferroelectric random access memories (FRAM).1- 4 In metal-ferroelectricsemiconductor field effect transistor (MFSFET) for FRAM, a high dielectric constant in ferroelectric materials decreases an applied voltage in ferroelectric materials, whereas an applied voltage in a low dielectric interfacial layer is increased. This causes device degradations such as charge injection and a high leakage current. To resolve these problems, ferroelectric materials with a low dielectric constant and new buffer layers at the ferroelectric/Si interface have been extensively investigated. 5 6 Among the ferroelectric thin films, YMnO 3 has been proposed as a promising ferroelectric material for metal-ferroelectricsemiconductor (MFS) structures.7'-' 0 The YMnO3 has a hexagonal structure and a unipolarization direction along [0001]. The YMnO3 thin film has low dielectric permittivity (e = 30 at RT), which is a great advantage for a device directly on silicon.' So far, considerable effort has been focused on the electrical properties, such as memory window and leakage current.'-" However, although the crystallization behavior and the crystallized atomic structure of the YMnO 3 thin films are important to evaluate and to improve the electrical properties of, they have not been sufficiently studied. Moreover, there are no studies concerning a relationship between stress and crystallization in the YMnO_ thin films. In this study, the atomic structure of the YMnO_ thin films has been characterized with high-resolution transmission electron microscopy (HRTEM), and the stress in the YMnO3 thin films has been

R

mH. Results and Discussion
Figure I shows a cross-sectional dark-field (DF) TEM micrograph of the YMnO 3 /Si, which was observed using a YMnO3 (0004) diffracted spot. This figure shows that the 100-nm-thick YMnO3 thin film is composed of two distinct layers: a top layer of a c-axis-oriented YMnO 3 -40 nm thick, which looks bright in the (0004) DF image, and a bottom polycrystalline YMnO3 layer -60 nm thick. Figure 1 demonstrates that the YMnO3 thin film has been crystallized with the two layers, which have different crystallographic orientations. Figure 2 shows an HRTEM micrograph of an interface between the c-axis-oriented YMnO3 layer and the polycrystalline YMnO 3 layer. In Fig. 2, the top region shows YMnO, {0002} lattice images with a distance of 0.57 nm. However, the bottom region does not show YMnO 3 {000h} lattice images. The YMnO3 {12121 plane in the polycrystalline layer is parallel to a {00021 plane in the c-axis-oriented layer. This abrupt change of the crystalline orientation in the YMnO 3 thin film during an RTP annealing is expected to relate to a composition difference or a stress effect between the two layers in the YMnO 3 thin film. To examine the composition difference between the two layers, energy-dispersive spectroscopy and auger electron spectroscopy have been used. However, no composition difference between the two layers was detected. Accordingly, it is expected that this two-layer crystallization in the YMnO 3 thin film is caused primarily by the stress effect. To investigate the stress effect on crystallization of the YMnO 3 thin films on silicon, we prepared three YMnO 3 thin films on a Si substrate, i.e., as-deposited amorphous YMnO3 , c-axis/amorphous YMnO3 , and c-axis/polycrystalline YMnO 3 thin films. The c-axis/ 149

H. U. Anderson-contributing editor

Manuscript No. 187305. Received November26, 2001; approved August 23,2002. This study was supported by the Ministry of Science and Technology through a Project for National Research Laboratory in Korea and a Collaborative Project for Excellence in Basic System IC Technology (SYSTEM IC 2010).

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Fig. 1. Dark-field TEM micrograph observed using the YMnO3 (0004) diffracted spot showing the two distinct layers in the YMnO 3 thin film on Si substrate.

I

0

Steps, arcsec

200

Fig. 3. High-resolution XRD showing the Si (004) rocking curves of as-deposited, c-axis/amorphous and c-axis/polycrystalline YMnO 3 thin films on Si (100) substrates.

Fig. 2. High-resolution TEM micrograph showing the interfacial microstructure between the c-axis-oriented YMnO 3 layer and the polycrystalline YMnO3 layer. amorphous YMnO 3 thin film is made by a rapid annealing process at 850°C for -30 s. The stress of polycrystalline thin films on a single-crystal substrate can be evaluated by HRXRD using a rocking curve of the substrate.' 2 Therefore, Si (004) rocking curves were measured using HRXRD to investigate the stress of the three YMnO 3 thin films. Figure 3 shows Si (004) rocking curves taken from the as-deposited amorphous YMnO3 sample. the c-axis/amorphous YMnO 3 sample, and the c-axis/polycrystalline YMnO 3 sample. The full width at half maximums (FWHMs) of the rocking curve from the as-deposited amorphous YMnO3 sample, the c-axis/amorphous YMnO 3 sample, and the c-axis/polycrystalline YMnO3 sample were 17.24, 38.64, and 17.33 arcsec, respectively. The FWHM of the c-axis/amorphous YMnO 3 sample was considerably broader; however, the FWHM of the c-axis/polycrystalline YMnO3 sample was nearly the same as that of the as-deposited sample. This result implies that the c-axis-oriented YMnO 3 layer induces a high stress, and the c-axis/polycrystalline YMnO 3 structure effectively reduces the stress. In our previous work,' 3 stress was more effectively relieved in polycrystalline YMnO 3 thin films than c-axis-oriented YMnO 3 thin films. Accordingly, to relieve the high stress of the c-axis-oriented YMnO 3 layer, the polycrystalline YMnO 3 layer was crystallized under the c-axis-oriented YMnO 3 layer. Figure 4 shows a schematic diagram of the crystallization mechanism in the YMnO3 /Si structure. The as-deposited amorphous YMnO3 (a-YMnO 3 ) thin film has started to be crystallized from the surface with a (0001) orientation. Because YMnO 3 has a hexagonal structure, a (0001) plane of YMnO 3 is a closest packing

plane and has low energy. Therefore, at free surface of the film, a (0001) plane has been preferably crystallized. Our previous report' 3 demonstrated that purely c-axis-oriented YMnO3 thin films on silicon substrate were cracked. For a crack formation, thin film has to have a tensile stress. The thermal expansion coefficients along the a-axis and c-axis of YMnO3 thin film and silicon are-18.5 X 10- 6 /SC,3.5 x 10-6/0C,and2.33 X 10-6/IC, respectively.14 Because the thermal expansion coefficient along the a-axis of YMnO 3 thin film has a negative value, when the temperature is increased, the c-axis-oriented YMnO 3 layer has high-tensile stress. Therefore, to relieve high-tensile stress, the crystallization with a c-axis-preferred orientation is suppressed. and the crystallization with a random orientation is favorable in the YMnO3 film. Accordingly, the polycrystalline YMnO3 layer is formed under the c-axis-oriented YMnO3 layer, as shown in Fig. 4. With falling temperature, the c-axis-oriented YMnO3 layer has compressive stress, but it is relieved by the polycrystalline YMnO 3 layer. IV. Conclusion

During the crystallization of an as-deposited amorphous YMnO3 thin film on Si (100) substrate at 850°C in N ambient, the 2 YMnO3 thin film crystallized with two distinct layers. Transmission electron microscopy revealed that the two layers were a c-axis-oriented YMnO3 layer and a polycrystalline YMnO 3 layer. Moreover, this c-axis/poly-YMnO 3 structure effectively relieved the stress, which was confirmed by high-resolution X-ray diffraction. In this two-layer YMnO 3 structure, the improvement of a ferroelectric property, because of the c-axis-oriented layer and the

Fig. 4. Schematic diagram showing the crystallization mechanism of the YMnO 3 thin films on silicon substrates.

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Two-Layer Crystallization of Amorphous YMnO_ Thin Films on Si (100) Suibstrates

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relief of high stress, is expected. Accordingly, the YMInO 3 thin films could be differently crystallized by the control of the stress in YMnO_ thin films. References
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TITLE: Two-Layer Crystallization of Amorphous YMnO3 Thin Films on Si (100) Substrates SOURCE: Journal of the American Ceramic Society 86 no1 Ja 2003 PAGE(S): 149-51 WN: 0300102109024 (C) Copyright by the American Ceramic Society. All rights reserved

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