Chemical Physics Letters 384 (2004) 134138 www.elsevier.

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A local structure of low coverage Ni species on the a-Al2O3 (0 0 0 1) surface a polarization dependent EXAFS study
Kaoru Ijima a,c, Yuichiro Koike a, Wang-Jae Chun a,b, Yukinori Saito c, Yasuhiro Tanizawa d, Takafumi Shido d, Yasuhiro Iwasawa d, Masaharu Nomura e, Kiyotaka Asakura a,*
b a Catalysis Research Center, Hokkaido University, Kita 21-10, Kitaku-ku, Sapporo 001-0021, Japan Core Research for Evolutional Science and Technology, Japan Science and Technology Corporation, Sapporo 060-0811, Japan c Department of Electronic Engineering, Yamanashi University, Kofu 400-8510, Japan d Department of Chemistry, Graduate School of Science, The University of Tokyo, Tokyo 113-0033, Japan e Photon Factory, Institute of Materials Structure Science, Tsukuba 305-0801, Japan

Received 30 August 2003; in nal form 28 November 2003 Published online:

Abstract The geometrical structure of a low coverage Ni species on an a-Al2 O3 (0 0 0 1) single crystal surface has been studied using a polarization-dependent total reection uorescence extended X-ray absorption ne structure (PTRF-EXAFS) spectroscopy to reveal the bonding feature between the metal and the oxide surface. The Ni species on the a-Al2 O3 (0 0 0 1) surface is atomically dispersed with a NiO distance at 0.198 0.003 nm. The adsorption site is determined to be a threefold oxygen site on top of a deep Al atom accompanied with a relaxation of the nearest neighbor oxygen atoms. 2003 Elsevier B.V. All rights reserved.

1. Introduction Interaction between metal and oxide surface is not only interesting in fundamental science but also an important issue in many technological and industrial processes such as catalyses, sensors, electronic devices, electrodes, adsorption on soils and so on. However, the basic researches using single crystal oxides have just recently been started because of their low electric conductivity [14]. Although new techniques such as surface X-ray diraction [5] and scanning probe microscopy [6] have provided information about the structures at the metaloxide interface, yet it is still dicult to obtain the bonding feature between metal and oxide surface experimentally. We have not had sucient answers to the following fundamental questions, yet: 1. Do metal atoms preferably interact with O2 on the surface?
*

Corresponding author. Fax: +81-11-706-3671. E-mail address: askr@cat.hokudai.ac.jp (K. Asakura).

2. If so, what type of bonding is present between them? Is there a charge transfer? 3. Or do metal atoms interact with cations? EXAFS (extended X-ray absorption ne structure) refers to the oscillations appearing 1001000 eV above an X-ray absorption edge and provides information about a local structure around an X-ray absorbing atom [7]. Many EXAFS works have been applied to metal species dispersed on powder oxides. However, it is not easy to elucidate the metaloxide interface structure because conventional EXAFS gives average structure of metal species in all directions. On the other hand, polarization dependent EXAFS can give structures selectively along the direction of an X-ray electric vector. When one measures EXAFS of metal species on a at substrate with dierent polarizations, one can have the pseudo-three dimensional information. It will give us a new class of information about the structure of metal species on oxide surfaces. A polarization dependent total reection uorescence EXAFS (PTRF-EXAFS) technique is suitable to study the structure of metals

0009-2614/$ - see front matter 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.cplett.2003.12.011

K. Ijima et al. / Chemical Physics Letters 384 (2004) 134138

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Fig. 1. An Al-terminated a-Al2 O3 (0 0 0 1) surface. The atomic positions are corresponding to those of the a-Al2 O3 bulk crystal. Three types of threefold hollow site are indicated as site-1, site-2 and site-3, respectively. (a) Top view, (b) side view. A thick-line box indicates the Al2 O9 dimer unit.

UHV preparation chamber and cleaned by further annealing at 873 K under 5 108 Pa. We obtained the aAl2 O3 (0 0 0 1) surface with a (1 1) LEED pattern and little C1s peak detected by XPS. Ni was deposited on the a-Al2 O3 (0 0 0 1) by resistive heating of a Ni-coated W wire. The Ni coverage was monitored by XPS using Ni2p3=2 peak. Inection point in the Ni2p3=2 peak intensity plots against the deposition time is tentatively used as a denition of 1 ML. The sample was transferred from the preparation chamber to a measurement chamber through a transfer chamber. In the UHV measurement chamber [13], a 6-axis goniometer was installed to adjust the total reection conditions and the sample orientations against the polarization vector. The base pressure was 3 108 Pa. EXAFS data were accumulated at BL9A of the Photon Factory in Institute for Material Structures Science (KEK-IMSS-PF) which was operated at 2.5 GeV400 mA [14] (2000G276). X-rays were monochromatized by Si(1 1 1) double crystals and focused onto the sample with the double bent conical mirrors. The size of X-ray was limited with a pin-hole to avoid undesired radiations other than the sample surface. The uorescence signals were detected by a 19-element pure Ge solid state detector (Canberra, SSDGL0110S). We measured the polarization dependent EXAFS spectra in two directions. One was the polarization vector parallel to the surface, denoted as s-polarization and the other was perpendicular to the surface, denoted as p-polarization.

3. Results and discussion We found the EXAFS oscillations characteristic to a NiNi bond in samples with more than 0.2 ML Ni deposition, indicating the formation of Ni metal clusters [15]. At 0.04 ML, no NiNi distance was found in two directions and Ni was atomically dispersed. Figs. 2a and 3a show the k-weighted EXAFS oscillations of the sample with 0.04 ML Ni loading for s- and p-polarizations, respectively. Main oscillations damped in a high k-region, indicating the presence of low Z elements in the rst nearest neighbor. The amplitude around k 60 nm1 was stronger in the spectrum of p-polarization than that of s-polarization. The surface structure of the clean a-Al2 O3 (0 0 0 1) surface was studied by LEED, ion scattering and grazing incidence X-ray scattering. It is demonstrated that a-Al2 O3 (0 0 0 1) is terminated with an Al layer as shown in Fig. 1 [1618]. This termination provides an autocompensated surface. Thus the exposed elements on the a-Al2 O3 (0 0 0 1) surface are both O and Al atoms, with which Ni could directly interact. We carried out curve tting analyses by assuming two possible nearest neighbors (O and Al). We had much better tting results when the rst shell was assumed to be oxygen. The curve tting results gave the NiO distance

highly dispersed on single crystal oxide surfaces [811]. The total reection tremendously reduces X-ray scattering from the bulk and increases surface sensitivity. The uorescence detection mode expands a lower detection limit of EXAFS. In this work we have investigated the structure of Ni on an a-Al2 O3 (0 0 0 1) single crystal especially in its low coverage region to reveal the metaloxide interface structure at the initial stage of the Ni overlayer growth. The Ni on Al2 O3 is a catalytically important material with its high activity for CO and alkenes hydrogenation reactions [12]. The Ni on aAl2 O3 (0 0 0 1) system is also interesting from the fundamental point of view because the a-Al2 O3 (0 0 0 1) surface can provide two types of O threefold and a surface Al atom as possible adsorption sites for Ni as shown in Fig. 1.

2. Experimental An a-Al2 O3 (0 0 0 1) (20 20 1 mm3 ) single crystal was purchased from Earth Jewelry Co. The sample was rst treated at 1073 K for 3 h in air. Then it was put in a

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K. Ijima et al. / Chemical Physics Letters 384 (2004) 134138

(a)
0.8 4 0.6 6 8

(b)10

(k)

(c)
0.4

(d)
0.2

(e)
0

-0.2

k / 10 nm-1

Fig. 2. Comparison of the observed p-polarization data (a) and the calculated data whose adsorption sites are site-1(b), site-2(c), site-3(d), and (e) the atomic model shown in Fig. 4, respectively.

1
(a)

0.8 4 0.6
(c)

(b)

10

0.4 0.2 0 -0.2

(d) (e)

k / 10 nm-1
Fig. 3. Comparison of the observed s-polarization data (a) and the calculated data whose adsorption sites are site-1(b), site-2(c), site-3(d), and (e) the atomic model shown in Fig. 4, respectively.

to be 0.198 0.003 nm for both directions. The coordination number was 2.6 0.5 and 3.0 0.5 of s- and p-polarizations, respectively. The ratio of the coordination numbers of s- to p-polarizations was 0.87. This result indicated that the location of Ni was not an atop site of an oxygen atom which should give no NiO oscillation in the s-polarization. Considering the polarization dependence in coordination numbers, the Ni atoms were situated on a threefold oxygen hollow site. The a-Al2 O3 (0 0 0 1) surface has two types of threehold oxygen sites as shown in Fig. 1. In the a-Al2 O3 crystal, oxygen ions approximately form a hexagonal close packed array and the Al ions occupy two-thirds of the octahedral interstices. Two Al octahedra share an oxygen triangle and form an Al2 O9 dimer unit as shown in

Fig. 1b. The Al atoms are deviated from the center of the octahedral site keeping another Al at a distance of 0.279 nm. Each Al atom has a terminal oxygen triangle with the OO distance of 0.286 nm and a sharing oxygen triangle with the OO distance of 0.252 nm. Consequently, there are two types of oxygen triangles with dierent OO bond lengths (0.286 and 0.252 nm) on the surface, which are tentatively called as site-2 and site-3 as shown in Fig. 1, respectively. Ni could possibly be situated on the threefold oxygen at site-1 by removing a surface Al atom. A dierence of these sites is the position of Al atoms in the second layer. Under the site-2 and site-3, Al atoms are located at 0.084 and 0.133 nm below the surface oxygen plane of an ideal bulk aAl2 O3 , respectively. Recent surface X-ray diraction indicated the relaxation of Al atoms in the surface region [17]. Al atoms at site-2 and site-3 are located at 0.097 and 0.169 nm below the surface oxygen layer, respectively. On the other hand no Al is found under the Ni at the Al-defective site-1. We carried out further analyses including Al atoms with their NiAl distances less than 0.37 nm using FEFF8 [19] and a real space model structure [20,21]. The second nearest O atoms could not be included in the calculation because of their small contributions to EXAFS oscillations. We postulated an ideal Al-terminated a-Al2 O3 (0 0 0 1) surface with no reconstruction as an initial structure, the atomic positions of which were given in the left side of Table 1. We put a Ni atom in the position of the Al-defective site1, site-2 and site-3 to fulll the NiO distance to be 0.198 nm and then we calculated the XAFS oscillations. But no good agreement was found in any of the model structures as shown in Figs. 2bd and 3bd. Then we allowed the positions of the nearest neighbor oxygen atoms and the Al atoms to move from the ideal positions but keeping the threefold symmetry. Finally we found a structure which well reproduced the EXAFS oscillations for both directions as shown in Figs. 2e and 3e. The atomic coordinates of O and Al were listed in the right side of Table 1. Model structure was given in Fig. 4a. We have three types of Al atoms included in this calculation; surface Al atoms, the second and the third layer Al atoms which were denoted as Al1, Al2 and Al3 in Fig. 4a, respectively. The Ni atom was located at the threefold oxygen site with NiO distance at 0.198 nm. An Al atom called as Al3 was found 0.278 nm under the Ni. Thus the Al-defective site-1 is not appropriate for the adsorption site of the Ni atom because there is no Al under it. Since the positions of Al2 and Al3 were well corresponding to the positions when Ni atom adsorbed on the site-3, we have proposed that the site-3 should be the most plausible site. Moreover, the site-3 corresponds to the imaginary Al position in the next Al layer over the a-Al2 O3 (0 0 0 1) surface as shown with the broken circle in Fig. 4. The Ni position is 0.109 nm above the center of the threefold site. The oxygenoxygen distances are

(k)

K. Ijima et al. / Chemical Physics Letters 384 (2004) 134138 Table 1 Assumed atomic position of Ni on a-Al2 O3 for the FEFF8 calculation Atoms Ideal Al-terminated Al2 O3 surface x Ni O O O Al1 Al1 Al1 Al2 Al2 Al2 Al3 0.0000 0.126 )0.126 0.275 )0.137 )0.137 0.137 )0.275 0.137 0.000 y 0.146 )0.073 )0.073 0.000 0.238 )0.238 0.238 0.000 )0.238 0.000 z 0.000 0.000 0.000 0.084 0.084 0.084 )0.084 )0.084 )0.084 )0.133 Atomic position after Ni deposition x 0.000 0.000 )0.143 0.143 0.275 )0.137 )0.137 0.137 )0.275 0.137 0.000 y 0.000 0.165 )0.083 )0.083 0.000 0.238 )0.238 0.238 0.000 )0.238 0.000 z 0.109 0.000 0.000 0.000 0.050 0.050 0.050 )0.133 )0.133 )0.133 )0.169

137

(a)

Al1 O Al2 O1 Al1 O O1 Ni,Al3

Al2 O Al1 O1 Al2

(b)

Al1 O Al2 O1 Al1 O O1 Ni,Al3

Al2 O Al1 O1 Al2

An Al position of the imaginary next layer Ni O O1 Al1 O1 O 0.109 0.050 0.000 O Al2 Al3 -0.133 -0.169 Al2 Al3 O1 Ni

An Al position of the imaginary next layer 0.109 Al1 O1 O 0.050 0.000 -0.036 -0.133 -0.169 scale : nm

Fig. 4. A proposed structure around the absorbed Ni: (a) without the upward shifts, (b) with the upward shifts of the oxygen atoms at site-3. Circles with broken lines indicate bulk positions. Another circle with a broken line above the site-3 corresponds to the imaginary Al position of the next Al layer.

expanded to 0.286 nm from 0.252 nm, an original value of the site 3 before the Ni adsorption, resulting in the O NiO angle nearly 90, which is often found in Ni2 compound. Maybe such expansion of the oxygen atoms will induce extra repulsion from surrounding oxygen atoms in the rst layer and is energetically unfavorable. This repulsive force can be liberated in the mechanism described later. In this structure the Al1, Al2 and Al3 are located at the positions lower than the bulk positions by 0.034, 0.049 and 0.036 nm and the positions proposed by recent surface X-ray diraction by )0.009, 0.036 and 0.036 nm, respectively [17]. The downward shifts of Al2 and Al3 may create stresses in the Al2 O3 bulk. Here we propose another relaxation around the Ni atom. If we assume the upward movement of the Ni, the

O atoms at the site-3 by 0.036 nm, Al2 and Al3 will remain at the positions determined by the surface X-ray diraction before the Ni adsorption as shown in Fig. 4b. Consequently, the stresses would not be created in the Al2 O3 bulk accompanied by the Ni adsorption and movements of Al2 and Al3. The upward shift could also reduce the stress caused by the expansion of the surface oxygen atoms at the site-3 mentioned above. The NiO distance is 0.198 nm which is similar to those found in Ni2 compounds like Ni(OH2 )2 . This 6 bond length indicates that the interaction between Ni and O should be the chemical bonding accompanied by the charge transfer. Ma et al. [22] have carried out a DFT calculation on the same NiAl2 O3 system. They found that the adsorption site of Ni was a threefold oxygen site,

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K. Ijima et al. / Chemical Physics Letters 384 (2004) 134138 [4] C.C. Chusuei, X. Lai, K. Luo, W. Goodman, Top. Catal. 14 (2001) 1. [5] G. Charlton, P.B. Howes, C.A. Muryn, H. Raza, N. Jones, J.S.G. Taylor, C. Norris, R. McGrath, D. Norman, T.S. Turner, G. Thornton, Phys. Rev. B 61 (2000) 16117. [6] C.L. Pang, S.A.H.H. Raza, G. Thornton, Surf. Sci. 460 (2000) L510. [7] Y. Iwasawa (Ed.), X-ray Absorption Fine Structure for Catalysts and Surfaces, World Scientic, Singapore, 1996. [8] S.M. Heald, E. Keller, E.A. Stern, Phys. Lett. 103A (1984) 155. [9] K. Asakura, M. Shirai, Y. Iwasawa, Catal. Lett. 20 (1993) 117. [10] S.N. Towle, G.E. Brown, G.A. Parks, J. Colloid Inter. Sci. 217 (1999) 299. [11] K. Asakura, W.-J. Chun, Y. Iwasawa, Top. Catal. 10 (2000) 209. [12] G. Ertl, H. Knozinger, J. Weitkamp (Eds.), Handbook of Heterogeneous Catalysis, Wiley-VCH, Weinheim, 1997. [13] W.J. Chun, Y. Tanizawa, T. Shido, Y. Iwasawa, M. Nomura, K. Asakura, J. Synchrotron Rad. 8 (2001) 168. [14] M. Nomura, A. Koyama, J. Synchrotron Rad. 6 (1999) 182. [15] K. Ijima, W.J. Chun, Y. Koike, K. Asakura (to be submitted). [16] J. Ahn, J.W. Rabalais, Surf. Sci. 388 (1997) 121. [17] P. Guenard, G. Renaud, A. Barbier, M. Gautier-Soyer, Surf. Rev. Lett. 5 (1997) 321. [18] C.F. Walters, K.F. McCarty, E.A. Soares, M.A. Van Hove, Surf. Sci. 464 (2000) L732. [19] J.J. Rehr, R.C. Albers, S.I. Zabinsky, Phys. Rev. Lett. 69 (1992) 3397. [20] W.-J. Chun, K. Asakura, Y. Iwasawa, J. Phys. Chem. 102 (1998) 9006. [21] Y. Tanizawa, T. Shido, Y. Iwasawa, M. Nomura, W.-J. Chun, K. Asakura, J. Phys. Chem. (in press). [22] Q. Ma, K. Klier, H. Cheng, J.W. Mitchell, K.S. Hayes, J. Phys. Chem. 105 (2001) 2212.

which agrees with our XAFS results. But there are great discrepancies in the NiO and NiAl distances which were 0.227 and 0.263 nm in their work. When the NiAl distance of 0.263 nm was assumed, we could not reproduce the EXAFS oscillation in the p-polarization. This dierence comes from electronic states. The Ni atom in their calculation had a neutral charge and had weak interaction with the surface in the calculation [22]. But in our XAFS results, the Ni is bound to the surface through a rather strong NiO bond. Further calculations must be necessary including the structural information given in this work. This work has rst demonstrated that the adsorption site of Ni to the Al2 O3 (0 0 0 1) surface prepared under UHV conditions is a threefold oxygen site and not to the surface or subsurface cation site. The bonding between Ni and O atoms on the Al2 O3 is a rather strong chemical bond. We have proposed the surface relaxation around the Ni atom that the threefold oxygen triangle is expanded with its side from 0.252 to 0.286 nm and is upward shifted by 0.036 nm. References
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