NANO LETTERS

Self-organized Fabrication of Ordered Nanostructures of Variable Periodicity on Nonstoichiometric Metal Oxide Materials
Toshitaka Kubo and Hisakazu Nozoye*
National Institute of AdVanced Industrial Science and Technology (AIST), Central 5, 1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
Received July 10, 2002; Revised Manuscript Received August 5, 2002

2002 Vol. 2, No. 10 1173-1175

ABSTRACT
We report the controlled fabrication of self-organized nanostructures by the use of solid-state reaction between a deposited film and a metal oxide single-crystal substrate. Long-range ordered nanocrystals are formed by the reaction of MgTiO on MgO(001) and BaTiO on TiO2(001). The size and the periodicity of the nanocrystals can be changed by deposition conditions.

Recently, there has been considerable interest in the fabrication of nm-order super lattices, such as quantum well structures. In fact, nm-order structures are considered as the key for many applications in data storage, functional devices, communications and biotechnology. For nm-order regions, quantum-physical properties depend strongly on its geometric parameters, such as size, shape, density and uniformity. The nanostructures, which are randomly distributed, fluctuate in size and have an unchanged periodicity, give significant limitations for applications. Many research groups have been trying to fabricate the structures by various methods;1-7 however, the controlled fabrication is still a daunting challenge and remains as one of the major problems for the study of nanofabrication. Here we show ordered and flexible nanostructures synthesized by the use of nonstoichiometric behaviors of the metal oxides. Experiments were carried out in an ultrahigh vacuum noncontact atomic force microscopy (UHV NC-AFM, JEOL) with a base pressure of 1.4 10-8 Pa. We used MgO(001) single-crystal substrates of 7 1 1 mm3 cleavaged in air just before experiments and TiO2(001) single-crystal substrates of 7 1 0.5 mm3. The substrate was directly mounted on a silicon heater and heated at 900 C for an hour under UHV. Temperature of the substrate was measured with an optical pyrometer. The procedure for the synthesis of Mg-Ti-O nanocrystals was as follows. Ti atoms were supplied in an O2 atmosphere of 2.6 10-6 Pa on MgO(001) at 600 C. To progress the solid-state reaction between the deposited film and the single-crystal substrate, the sample
* Corresponding author. Phone: (+81)-298-61-4527. Fax: (+81)-29861-4504. E-mail: h.nozoye@aist.go.jp 10.1021/nl025695b CCC: $22.00 Published on Web 08/22/2002 2002 American Chemical Society

Figure 1. NC-AFM images (500 500 nm2) of the Mg-Ti-O nanocrystals formed on MgO(001) with different conditions. Ti atoms were deposited for 10 min at a rate of (a) 1.0 and (b) 0.2 nm/min in an O2 atmosphere of 2.6 10-6 Pa maintained at 600 C and kept for 10 min after stopping the Ti supply. (a) and (b) Schematic models of (a) and (b).

was kept at 600 C for 10 min after stopping the Ti supply. For the synthesis of Ba-Ti-O nanocrystals, Ba atoms were deposited on TiO2(001) at room temperature and the sample was subsequently heated at 1000 C for 1 min. Figures 1a and b show the surface morphology after the growth of Mg-Ti-O on MgO(001). Rectangular crystals along the [110] or [110] directions were observed. The step h height of each crystal was always 0.2 nm. Schematic models are shown in Figure 1a and b. When the titanium deposition rate was 1.0 nm/min, as shown in Figure 1a, the width and

Figure 2. Scanning tunneling microscopy (STM) images (300 300 nm2) of the Ba-Ti-O nanocrystals formed on TiO2(001). (a) Ba atoms were deposited at room temperature and subsequently heated at 1000 C in UHV. (b) After two cycles of the treatments of a. (a) and (b) Schematic models of (a) and (b).

Figure 3. Schematic representations of (a) layer plus island growth mode (Stranski-Krastanov) and (b) buffer-layer plus island growth mode.

the periodicity of the rectangular crystals were 10 and 18 nm, respectively. On the other hand, when the titanium deposition rate was relatively slow (0.2 nm/min), as shown in Figure 1b, the width and the periodicity became relatively large (15 and 21 nm, respectively). These suggest that the size of the nanostructures is changed by the rate of the metal supply. In our previous work, it was concluded that nonstoichiometric Mg-Ti-O spinel(001), whose surface termination layer was Mg, was epitaxially formed with its crystal axes in accord with the MgO(001) substrate by solidstate interface reaction.8 As Mg-Ti-O spinel (Mg1+xTi2-xO4; 0 < x < 1) is composed of Mg and MgxTi2-xO4 alternative layers with the distance of a/8 (a 0.84 nm) in the 001 direction, the step height of 0.2 corresponds to the distance between the Mg layers. Figures 2a and b show the surface morphology after the growth of Ba-Ti-O on TiO2(001). Rectangular crystals along [100] or [010] directions were observed. When the amount of the deposited Ba atoms was relatively small, nanocrystals were mainly grown at the step edge and defective site, as shown in Figure 2a. In this deposition condition, the width, height and the periodicity of the rectangular crystals were 5, 1, and 7 nm, respectively, as shown in Figure 2a. When the amount of the deposited Ba atoms was increased, the size of the nanocrystals was increased (width: 7 nm, height: 1.5 nm, and periodicity: 10 nm), as shown in Figure 2b and b. With progressing the solid-state reaction, many etch pits were observed among the nanocrystals, suggesting that the Ti and O atoms were supplied from the TiO2(001) substrate for the formation of the Ba-Ti-O crystal. In this image, the widths of the rectangular crystals were always a multiple of the narrow one. We can see the thick crystals (denoted by B and C), whose widths were double and triple of the narrow one (denoted by A). It is noted that, depending on the different deposition conditions, the periodicity of the ordered nanocrystals is changed from several nm to 50 nm (not shown).
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For the previously reported nm-order structures,1-7 there are several critical problems. (1) The size distribution is generally broad. (2) As the periodicity is strongly limited by the substrate and (or) the deposited materials, the distance between nanostructures is hard to change. (3) Existence of defects lowers the quality of arrangements. In contrast, using solid-state reaction, highly ordered nanocrystals of variable periodicity are obtained. The growth mechanism is understood by the strain induced Stranski-Krastanov (SK: layer plus island growth) mode. The SK growth mode is explained by assuming a lattice mismatch between deposited film and substrate, as shown in Figure 3a. The lattice of the film has a tendency to adjust to the substrate lattice, but with the expense of elastic deformation energy. The transition from layer-by-layer to island growth occurs when the elastic strain energy exceeds the adhesion energy within the deposited material.9 As the elastic tensile deformation provides preferential nucleation sites of the 3D islands, the regimented arrangement of the 3D islands is formed.7 In the case of the metal oxide nanocrystals formed by the solid-state reaction, film growth involves the interdiffusion at the interface. It is considered that strained buffer layers, which determine the size of the nanocrystals, are formed, as shown in Figure 3b. It is well known that the lattice constant of the metal oxide is changed depending on its stoichiometry.10 Depending on the progress of the solid-state reaction, the elastic strain inside the buffer layers changes. This may result in changes in the size and periodicity of nanocrystals. In addition, it is considered that most of the preexisting surface defects on the substrate, which are crucial problems for the formation of highly ordered 3D islands in the SK growth mode, disappeared during solid-state reaction. As many metal oxides contain ordered defects inside the crystals forming long-range intermediate structures in order to relieve the crystalline strain force,10 the formation of ordered nanocrystals may be based on the natural tendency of the metal oxide materials. The metal oxides constitute a diverse and fascinating class of materials. The ordered nanocrystals will play crucial roles in the field of nanotechnology.
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Figure 4. (a) Schematic model of the self-assembled quantum dots using variable template lattices. (b) NC-AFM images (100 67 nm2) of Ba atoms deposited on the Ba-Ti-O nanotemplate lattice (periodicity: 5 nm).

has some advantages in its uniformity and variability. Figure 4b shows the surface morphology of the Ba atoms deposited on the Ba-Ti-O nanostructure, Ba clusters arranged along the template rows are observed. Using these methods, we can build various nanostructures with sizes that are much smaller than photolithographic limitation. In conclusion, we succeed to obtain ordered nanostructures, with size distributions that are considerably small and that have variable periodicity. The results may pave the way for the nanofabrication and promote the study of quantum phenomena. Acknowledgment. This work was supported in part by Grants-in-Aid from Ministry of Education, Culture, Sports, Science and Technology. References
(1) Chambliss, D. D.; Wilson, R. J.; Chiang, S. Phys. ReV. Lett. 1991, 66, 1721-1724. (2) Zhu, J.-H.; Brunner, K.; Abstreiter, G. Appl. Phys. Lett. 1998, 73, 620-622. (3) Leon, R. et al. Appl. Phys. Lett. 1999, 74, 2301-2303. (4) Nikoobakht, B.; Wang, Z. L.; El-Sayed, M. A. J. Phys. Chem B. 2000, 104, 8635-8640. (5) Ma, W. et al. Appl. Phys. Lett. 2001, 78, 1297-1299. (6) Zhang, Y. P.; Yan, L.; Xie, S. S.; Pang, S. J.; Gao, H.-J. Surf. Sci. 2002, 497, L60-L64. (7) Teichert, C. Phys. Rep. 2002, 365, 335-432. (8) Kubo, T.; Nozoye, H. Thin Solid Films 2001, 394, 151-158. Kubo, T.; Nozoye, H. Appl. Surf. Sci. 2002, 188, 545-549. (9) Luth, H. Surfaces and Interfaces of Solid Materials, 3rd ed.; Springer Verlag Berlin, 1997. (10) Rao, C. N. R.; Raveau, B. Transition Metal Oxides; VCH: New York, 1995.

The nanostructures have been employed as template lattices for self-assembled quantum dots, as shown in Figure 4a. As self-assembled fabrication of ordered quantum dots is a promising approach for high-throughput nanofabrication, many research groups have been trying to fabricate by the use of Vollmer-Weber (VW: island growth) mode. When metal atoms are deposited on a substrate surface, metal atoms migrate to find stable adsorption sites, such as step, kink, defect, and a site of the surface reconstruction. The case that the interaction between deposited atoms is stronger than that between deposited atoms and substrate leads to 3D island growth. Then, the regimented arrangement of the 3D islands is controlled by the initial stable adsorption sites, such as Au(111) herringbone structure,1 Si(111)-7 7 structure6, steps of vicinal Si(001),2 and steps of vicinal GaAs(001).3 Although, self-assembled quantum dots are obtained using these template lattices, these are very limited and hard to change sizes. Pattern formation using solid-state reactions

NL025695B

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