Orientation-Dependent Structural Properties and Growth Mechanism of ZnO Nanorods

H.-J. Yu1, E.-S. Jeong1, S.-H. Park2, S.-Y. Seo2, S.-H. Kim2, S.-W. Han1
Division of Science Education and Institute of Proton Accelerator, Chonbuk National University, Jeonju 561-765, Korea 2 Department of Materials Science and Engineering, Pohang University of Science and Technology, Pohang 790-784, Korea
Abstract. We present the local structural properties of ZnO nanorods studied by using extended x-ray absorption fine structure (EXAFS). Vertically aligned ZnO nanorods were fabricated on Al2O3 substrates by a catalyst free metal organic chemical vapor deposition (MOCVD). The polarized EXAFS measurements on the ZnO nanorods were performed at Zn K-edge. The polarized EXAFS study revealed that the nanorods had a wurtzite structure, and that there were substantial amount of structural disorders in Zn-O pairs in the beginning of the nanorod growth. The EXAFS measurements revealed that the orientation-dependent disorders of the Zn-O pairs were directly related to the growth mechanism and crystal quality of the ZnO nanorods. Keywords: EXAFS, ZnO, nanorod, growth mechanism, MOCVD PACS: 61.60.Ht, 61.46.Hk, 61.43.Dq
1

INTRODUCTION
Semiconducting nanostructures have attracted considerable attention for their practical applications to nanometer-scale electronics and photonics as well as fundamental academic research. ZnO is a candidate material for room temperature UV applications due to 3.36 eV band gap energy and 60 meV exciton binding energy at room temperature. In addition, it is relatively easy to fabricate vertically aligned ZnO nanorods with various fabrication techniques [1-5]. The ZnO nanorods were intensively studied for its practical applications, AFM cantilevers [6], gas sensors [7,8], nanotransistors [9], logic gate device [10], and UV light emitting diodes [11]. Many previous studies attempted to understand the growth mechanism of ZnO nanorods [12-15]. However, the growth mechanism is still unclear. We investigated if structural stress due to lattice mismatch between the ZnO and substrates play a role in the ZnO nanorod growth. We employed polarized extended x-ray absorption fine structure (EXAFS) which can describe the angles and distances of neighboring atoms from a probe atom [16], to investigate the orientationdependent residual strain in ZnO nanorods. Two independent EXAFS measurements from the vertically aligned ZnO nanorod arrays with different lengths were made with the x-ray polarizations parallel and perpendicular to the nanorod length direction. Both sets of EXAFS data were simultaneously fitted with the same parameters and the orientation-dependent structural properties of the ZnO nanorods were obtained.

EXPERIMENTAL
ZnO nanorod arrays were fabricated using metal-organic chemical vapor deposition (MOCVD) on Al2O3(0001) substrates. The substrate temperature was maintained at 300 450 oC and the growth rate was about 10 nm per minute. To investigate the structural residual strain in ZnO nanorods, we synthesized the ZnO nanorods with average length of 0.1, 0.2, 1.0 Pm on the Al2O3 substrates. The average diameters of the ZnO nanorods were 50 100 nm. Scanning electron microscope (SEM) images revealed vertically well-aligned ZnO nanorods. Highresolution x-ray diffraction (XRD) and high-resolution transmission electron microscope (TEM) measurements demonstrated that the ZnO nanorods were well-ordered single crystals. The EXAFS measurements at Zn K edge (9659 eV) with fluorescence and transmission modes for ZnO nanorods and powder, respectively, were made at

Author to whom correspondence should be addressed; Email: swhan@chonbuk.ac.kr.

CP879, Synchrotron Radiation Instrumentation: Ninth International Conference, edited by Jae-Young Choi and Seungyu Rah 2007 American Institute of Physics 978-0-7354-0373-4/07/$23.00

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beamline 3C1 of Pohang Light Source at room temperature. Incident x-ray energy was selected with a three-quarters tuned Si(111) double monochromator.

FIGURE 1. Total x-ray absorption from ZnO powder and (b), (c) orientation-dependent x-ray absorption coefficient of ZnO nanorods near Zn K-edge as a function of incident x-ray energy. For the orientation dependent EXAFS measurements, the electric field vector of the incident x-ray was aligned (b) parallel (H || c) and (c) perpendicular (H A c) to the ZnO nanorod length direction. (d) EXAFS (k ) from ZnO powder (1st) ZnO nanorods with lengths of 0.1 Pm (2nd, 5th), 0.2 Pm (3rd, 6th) and 1.0 Pm (4th, 7th) as a function of photoelectron wave vector described in the text. The 2nd-4th are for H || c and the last three are for H A c.

FIGURE 2. Magnitude of Fourier transformed EXAFS from the data of ZnO nanorods with 1.0 Pm length as a function of distance from a zinc atom. For the Fourier transformation, a Hanning window with a windowsill width of 0.5 -1 was used. Data in the range of r = 1.2 - 3.3 were fitted.

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TABLE 1. Results of EXAFS Analysis Zn-O(1) specimen length

N

Zn-O(2)
N

Zn-Zn(1) V2
N

Zn-Zn(2) V2
N

d
1.903(9) 1.939(5) 1.939(6) 1.939(5) 1.903(6)

V2
0.003(1) 0.0052(5) 0.0049(6) 0.0055(5) 0.003(1)

d
1.98(2) 2.018(7) 2.024(7) 2.018(6) 1.98(1)

d
3.206(1) 3.209(3) 3.209(5) 3.206(5) 3.216(10)

d
3.246(13) 3.255(4) 3.259(2) 3.257(4) 3.236(1)

V2
0.008(2) 0.0085(4) 0.0090(3) 0.0085(4) 0.004(1)

powder nanorods nanorodsx nanorods nanorods

0.1 Pm 0.2 Pm 1.0 Pm 0.5 Pm

1 1 1 1 1

3 3 3 3 3

0.003(1) 0.0045(6) 0.0027(6) 0.0028(6) 0.003(1)

6 6 6 6 6

0.008(4) 0.0088(4) 0.0089(4) 0.0085(4) 0.004(1)

6 6 6 6 6

Coordination number (N), bond length (d) and Debye-Waller factor (V2) of ZnO powder (top), ZnO nanorods/Al2O3 (middle three) and ZnO nanorods/GaN/Al2O3 (bottom). The EXAFS results of ZnO nanorods/Al2O3 at 300 K were determined by polarized-EXAFS measurements whereas those of ZnO powder at 300 K and ZnO nanorods/GaN/Al2O3 at 30 K were obtained from unpolarized EXAFS. S02 of 0.95(5) was used in the data fits. The R-factors of a goodness fit were 0.005, 0.006, 0.009, 0.012, and 0.007 for the specimens from the top, respectively.

RESULTS AND DISCUSSION

Figures 1 show the normalized total x-ray absorption and x-ray absorption coefficient from the ZnO powder and nanorods near the Zn K edge as a function of the incident x-ray energy. The near edge structures from the nanorods obviously show the dependence of the crystal orientations, and are very comparable with previous reports [17-19]. The EXAFS data were analyzed with the UWXAFS package [20] using standard procedures [16,18,19]. After the atomic background absorption P0 was determined using AUTOBK (part of the UWXAFS package), the EXAFS function, =P(E)/P0(E) - 1, was obtained. Figure 1 (d) shows the EXAFS from ZnO nanorods at the Zn K edge for H
2m ( E  E ) / = , where e 0 me is the electron rest mass, E is the incident photon energy and E0 is the edge energy. To minimize uncertainty only the EXAFS data in the k-range of 2.5 - 10.5 -1 were used for further analysis. Figure 2 shows the magnitudes of the Fourier transformed EXAFS data from the ZnO nanorods with different lengths. It should be noted that the peaks shifted by about 0.4 on the r-axis from their true bond lengths due to the phase shift of the back-scattered photoelectrons. The EXAFS data Fourier transformed to r-space were simultaneously fitted to the theoretical EXAFS calculations [21]. The fits included single- and multi-scattering paths. The data were fitted with a fully occupied model of a wurtzite structure, varying the bond lengths and Debye-Waller factors (V2, including thermal vibration and static disorder). The polarized-EXAFS data can independently determine the distances and V2s from the probe zinc atom to one O(1) located just below the Zn atom along the c-axis, three O(2)s located about 19o off from the Zn ab-plane, six Zn(1)s located at ~55o off from the ab-plane and six Zn(2)s located in the ab-plane. The fit results are summarized in Table 1. From the EXAFS data analysis, we observed that the V2s of Zn-O pairs in the ZnO film, with thickness of about 0.1 Pm, which was constantly observed in the beginning of the ZnO nanorod growth [22], had a substantial amount of disorders, compared with ZnO powder and high quality ZnO nanorods [18]. As ZnO formed into nanorods, the extra disorder in the Zn-O(2) pairs disappeared. However, the extra disorder in the Zn-O(1) pairs was observed in even 1 Pm nanorods. EXAFS revealed no extra disorders existing in all Zn-Zn pairs, comparing to ZnO powder counterpart. EXAFS results strongly suggested that the structural strain of Zn-O pairs in the ab-plane due to the lattice mismatch should be first relaxed for the ZnO nanorod growth. This result strongly suggested that the strain relaxation in ab-plane was the ZnO nanorod seeds of the Stranski-Krastanov growth mode. We also investigated the structural properties of the ZnO nanorods grown on Al2O3 with GaN interlayer. The EXAFS analysis results of the ZnO nanorods/GaN/Al2O3 are summarized in Table 1. The EXAFS measurements of ZnO nanorods grown on Al2O3 substrates with GaN interlayers demonstrated that the extra disorder of Zn-O(2) pairs as well as Zn-O(1) pairs was disappeared as the ZnO formed into nanorods. This provides more evidence that the strain relaxation of Zn-O(2) pairs are critical in the formation of ZnO nanorods. The XRD measurements (not shown here) of the ZnO nanorods showed that the lattice constant of the ZnO crystals was about 5.206 which corresponded well with that of ZnO bulk [18]. Interestingly, the full widths at half maximum (FWHM) of ZnO (0002) diffraction peak of ZnO nanorods grown on Al2O3 substrates was about three times larger than that of the ZnO nanorods grown on Al2O3 substrates with GaN interlayers. Comparing with EXAFS results, we concluded that the extra broadening of the diffraction peak in ZnO nanorods/Al2O3 was mainly affected by the disorder of Zn-O(1) pairs instead of Zn-Zn pairs.

|| c and the last three are for H A c , as a function of the photoelectron wave vector, k

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CONCLUSIONS
The polarized EXAFS technique was employed to investigate the growth mechanism of ZnO nanorods. Vertically aligned ZnO nanorods with various lengths were fabricated on Al2O3 substrates with and without GaN interlayers by MOCVD. The orientation-dependent structural properties of the ZnO nanorods were determined by the EXAFS at Zn K-edge. Polarized EXAFS measurements of ZnO nanorods grown on Al2O3 substrates revealed that a substantial amount of structural strain existed in the Zn-O pairs located in the ab-plane and that the strain disappeared as the ZnO formed into nanorods. Our observations present the strong evidence that the structural stress due to the lattice mismatch between nanorods and substrates dominantly influenced ZnO nanorod formation. We observed extra disorder existing in Zn-O(1) pairs of ZnO nanorods grown on the Al2O3 substrates, comparing with the ZnO nanorods grown on the GaN/Al2O3 substrates.

ACKNOWLEDGEMENTS
This work was supported by the Korea MOEHRD (KRF-2005-042-C00055), the Korea Basic Research Program (KOSEF-R01-2006-000-10800-0), the Korea MOCIE through the New Technology R&D Program, and the Korea MOST through PEFP User Program as a part of the 21C Frontier R&D Program. The EXAFS data were collected at 3C1 beamline of the Pohang Light Source.

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