INSTITUTE OF PHYSICS PUBLISHING Nanotechnology 17 (2006) 43174321

NANOTECHNOLOGY doi:10.1088/0957-4484/17/17/006

Controlled growth of high-quality TiO2 nanowires on sapphire and silica

Jung-Chul Lee1 , Kyung-Soo Park1 , Tae-Geun Kim2 , Heon-Jin Choi3 and Yun-Mo Sung1,4
Department of Materials Science and Engineering, Korea University, Seoul 136-713, Korea 2 Department of Electronic Engineering, Korea University, Seoul 136-713, Korea 3 School of Advanced Materials Science and Engineering, Yonsei University, Seoul 120-749, Korea E-mail: ymsung@korea.ac.kr
1

Received 27 May 2006, in nal form 15 July 2006 Published 8 August 2006 Online at stacks.iop.org/Nano/17/4317 Abstract The vapourliquidsolid (VLS) growth of TiO2 nanowires (NWs) was performed using a thermally evaporated Ti source and sputter-deposited Au catalysts under an O2 gas ow. High-density single-crystalline TiO2 NWs having the rutile structure were successfully grown on sapphire (single-crystal -Al2 O3 ) and quartz (amorphous SiO2 ) substrates. Ti buffer layers, deposited on the substrates to prevent undesirable reactions between the Ti vapour and substrates, were identied to promote the TiO2 NW growth by providing supplementary Ti vapour to the Au catalysts. Crystallinity of TiO2 NWs was investigated by x-ray diffraction (XRD) and their morphological features were characterized by eld emission scanning electron microscopy (FESEM). High-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) analyses reveal growth of the rutile NWs having twofold twin structures along the growth direction on Ti/sapphire and the defect-free single-crystalline rutile NWs on Ti/quartz substrates. TiO2 NWs grown on Ti/quartz showed a short-wavelength (402 nm) and high-intensity photoluminescence (PL) emission compared to those grown on Ti/sapphire substrates. By introducing a Ti buffer layer and using quartz substrates, the crystallinity and PL properties were successfully improved for VLS-grown TiO2 NWs. (Some gures in this article are in colour only in the electronic version)

1. Introduction
TiO2 is one of the most investigated oxide materials owing to its important role in applications related to semiconductor photocatalysts [13], gas sensors [4], optical devices [5], and solar cells [6]. The photochemical or photocurrent efciency of TiO2 is greatly inuenced by its crystal structure, particle size, surface area and porosity. With the rapid development of nanotechnology, TiO2 nanostructures in various forms are nding wider applications than before. Previous research results show that TiO2 can be synthesized into one-dimensional nanostructures including nanowires (NWs) by a template
4 Author to whom any correspondence should be addressed.

solgel method [7] and nanotubes by a chemical process method [8, 9]. However, these wet-chemical methods cause contamination problems, seriously deteriorating the electrochemical or optical properties of the TiO2 NWs, and the resulting NWs are in polycrystalline, showing strong negative effects due to grain boundaries. To date, only scattered results have been reported on the vapour phase synthesis and characterization of TiO2 NWs [1014]. To obtain highquality NWs through a vapour phase synthesis the relationship between substrates and NWs is of high importance. Si substrates have been used for the growth of TiO2 /SiO2 core/sheath nanocables [13]. On the other hand, the use of sapphire or quartz substrates would be highly desirable to 4317

0957-4484/06/174317+05$30.00

2006 IOP Publishing Ltd Printed in the UK

J-C Lee et al
-Al2O3

TiO2(110)

TiO2(101)

Sapphire substrate
-Ti TiO2(200)

TiO2(210) TiO2(111) TiO2(210)

Intensity (a.u.)

TiO2(101)

Quartz substrate
TiO2(211)

20

30

40 Two-theta

-Ti

50

TiO2(211)

60

Figure 1. XRD patterns of TiO2 NWs prepared via the VLS mechanism using sapphire and quartz substrates, respectively. Here, the TiO2 nanowires are in the rutile phase.

suppress the unwanted diffusion reactions possibly occurring between the Ti source and the substrates. In this study single-crystalline TiO2 NWs were prepared via the vapourliquidsolid (VLS) growth method using a thermal vapour transport of Ti on quartz and sapphire substrates, respectively. Ti buffer layers were introduced onto the surface of wafers to prevent undesirable diffusion reactions between the Ti vapour source and the substrates. To promote the growth of TiO2 NWs the Ti vapour must be consumed only for the VLS growth of TiO2 NWs. The crystal growth characteristics were investigated and compared for the rutile TiO2 NWs grown on Ti/sapphire and Ti/quartz substrates. The photoluminescence (PL) properties were also investigated for each sample and related with the crystallinity of TiO2 NWs.

2. Experimental details
Single-crystalline TiO2 NWs were prepared using a chemical vapour transport process by evaporating Ti metal powders. Sapphire ( -alumina) and quartz (silica) substrates, respectively, were selected for the growth of TiO2 NWs and prior to the NW growth they were subsequently cleaned by ultrasonication with acetone, isopropyl alcohol, and deionized water. A Ti buffer layer with a thickness of 500 nm was deposited on the each substrate by the RF-magnetron sputtering of a Ti target. An Au catalyst layer with a thickness of 50 nm was formed onto the Ti buffer layer by the subsequent RF-magnetron sputtering of an Au target in an argon gas atmosphere under the pressure of 5 103 Torr. Thermal vapour deposition was performed for the VLS growth of TiO2 nanowires on the Ti/sapphire and Ti/quartz substrates. An alumina boat loaded with pure Ti powder (99.9%, Kojundo Chemical, Saitama, Japan) was placed in the middle of a quartz tube furnace. Sapphire and quartz substrates, respectively, were placed over the alumina crucible with the polished side facing down to the Ti powder. Ar and O2 gases (99.9999%) were used as a carrier and a reactive gas, respectively, and their ow rates 4318

were 100 and 0.5 sccm, respectively. The time period for the growth of TiO2 NWs was 30 min and the substrate temperature was 1050 C. The tube furnace was then cooled down to room temperature and the Ar gas atmosphere was maintained. Field emission scanning electron microscopy (FESEM: Hitachi S4300, Tokyo, Japan) was employed to observe the morphological features and size distribution of TiO2 NWs. The crystallinity and growth orientation of TiO2 NWs were examined by x-ray diffraction (XRD: Rigaku 2000, Tokyo, Japan). Cu K radiation was used at 40 kV and 40 mA, and 2 scans covered from 20 to 60 at a step size of 0.5 min1 . High-resolution transmission electron microscopy (HRTEM: JEM4010, JEOL, Tokyo, Japan) was used at an accelerating voltage of 400 kV to investigate the crystal orientation, defects, and detail structure of TiO2 NWs. The optical characteristics of TiO2 NWs were examined by photoluminescence (PL: F-450 Hitachi, Tokyo, Japan).

3. Results and discussion

Trials to grow TiO2 NWs on Ti/Si substrates were not satisfactory, probably due to the loss in catalytic function of melted Au at high temperatures and the formation of TiSi alloy before nucleation and growth of TiO2 NWs [12]. On the other hand TiO2 NWs were successfully grown on the sapphire and quartz substrates, respectively. Figure 1 shows typical XRD patterns of TiO2 NWs grown on the sapphire and quartz substrates, respectively, by the thermal vapour transport process. XRD patterns of both TiO2 NWs clearly show formation of the rutile phase with a trace of -Ti, where the intensity of -Ti peak locating at 38 39 was much higher for the TiO2 NWs grown on sapphire substrates than for the NWs grown on quartz substrates. Also, it was observed that all the XRD peaks from the TiO2 NWs grown from sapphire substrates shifted to low 2 -values, which is most probably due to the TiO2 lattice expansion caused by the lattice mismatch between rutile and sapphire. This tensile strain applied to

Controlled growth of high-quality TiO2 nanowires on sapphire and silica

(a)

(b)

(c)

020

(d)

(e)

(f)
110

Figure 2. FESEM images of TiO2 NWs grown on (a) sapphire and (b) quartz substrates, respectively.

the TiO2 NWs could occur possibly due to the larger lattice parameter of the sapphire substrates compared to that of rutile. Using Braggs law and the relationship between the interplanar d -spacing and the Miller indices, the lattice parameters of the TiO2 NWs grown on sapphire and quartz were determined as a = 4.605 and c = 2.9613 A, and a = 4.576 and c = 2.951 A, respectively, obviously revealing the lattice expansion in TiO2 NWs grown on the sapphire substrates which have lattice parameters of a = 4.7851 and c = 12.992 A (JCPDS Card 46-1212). Figure 2 shows eld emission scanning electron microscopy (FESEM) images of the TiO2 NWs prepared on the different substrates. The FESEM image of the NWs grown on Ti/sapphire substrates (gure 2(a)) shows the uniform and high-density growth of TiO2 NWs with a diameter of 80 100 nm and a length of 15 m. Figure 2(b) shows an FESEM image of the TiO2 NWs grown on Ti/quartz substrates, having a diameter of 5080 nm and a length of 13 m. Those grown on the Ti/quartz substrates were straight and their surface was very smooth. The density of the TiO2 NWs grown on the sapphire substrates was higher than that of those grown on quartz, most possibly due to the effect of strain during nucleation. The strain energy applied to TiO2 nuclei with a critical size can lower the activation energy barrier for the formation of stable nuclei, resulting in the enhanced nucleation kinetics and thus the increased NW density on sapphire substrates. The TiO2 NWs grown on Ti/quartz substrates showed higher crystal growth rate compared to those grown on Ti/sapphire both due to the relatively low-density TiO2 nuclei and a higher vapour pressure from the Ti layer deposited on relatively rough quartz substrates. Surface roughness of quartz substrates can give higher surface area to the Ti buffer layer, also giving higher vapour pressure of Ti, especially at the convex areas of the

(g) TiO2 (020) TiO2 (101) 120

TiO2 (020) Al2O3 (0001)

Figure 3. TEM images ((a), (d)), SAED patterns ((b), (e)) and HRTEM images ((c), (f)) of TiO2 NWs grown on sapphire and quartz substrates, respectively. The SAED patterns of the NWs were taken along the [212] and [113] zone axes of TiO2 NWs, respectively, for (b) and (d). Schematic diagram showing the lattice match between the TiO2 NWs and sapphire substrates (f).

surface. The Ti layer is essential to supply supplementary Ti vapour pressure to penetrate into the Au catalyst and to acquire the VLS growth of the TiO2 NWs. Figure 3(a) shows a TEM image of individual TiO2 NWs prepared using sapphire substrates, revealing the formation of twins in the longitudinal direction of the NWs. The high interfacial energy caused by the lattice mismatch between the TiO2 NWs and sapphire substrates can be reduced forming the 4319

J-C Lee et al

Au layer

O2 Ti Sapphire (a) TiO2 layer

Ti vapour+O2
403

Ti Sapphire Intensity (a.u.) (b) Ti vapour+O2

415 450 465 nm

Ti vapour+O2 TiO2 layer Ti Sapphire (c) TiO2 layer Ti Sapphire

Quartz substrates Sapphire substrates

(d) 350 400 450 500 550 Wavelength (nm) 600 650

Figure 4. Schematic illustration of the growth procedure of twinned TiO2 NWs on sapphire substrates.

twin structures. The selected area electron diffraction (SAED) pattern shown in gure 3(b) was recorded along the [212] zone axis and it consists of overlapped patterns corresponding to each crystal locating at an either side of the mirror plane. The NWs have tetragonal rutile structures grown into the (020) lattice planes, showing (101) mirror planes. This twinned structure of NWs can play an important role in hastening the growth of NWs [15] together with the low Ti partial pressure. On the other hand TiO2 NWs prepared using quartz substrates with Au catalysts also showed high-quality single crystalline nature, as shown in gure 3(d). The SAED pattern shown in gure 3(e) was recorded along the [113] zone axis and it shows that the NWs have the tetragonal rutile structure grown to the (110) lattice planes. High-resolution TEM (HRTEM) observation of the NWs in gure 3(f) reveals that they are nearly perfect single crystalline and grown into the [110] orientation. Such a perfect single-crystalline nature is the consequence of crystal growth via the VLS mechanism. Furthermore, the free-standing nature of the TiO2 NWs grown on the amorphous quartz substrates allows excluding the effect of strain, which is generated from the lattice mismatch to the substrate and which acts as a driving force for the generation of defects. This should contribute to the preparation of single-crystalline defect-free TiO2 NWs. Figure 3(g) shows a schematic diagram of the lattice match between the NW TiO2 (002) twin planes and the substrate sapphire (0001) planes. By forming the twin structure the lattice mismatches between the two crystals can be reduced to 3.808 and 4.667% in the a -axis and c-axis, respectively. Here, a buffer layer-assisted VLS mechanism was proposed for the growth of twinned TiO2 NWs on the sapphire substrates (see gure 4). The Ti buffer layer and Au thin layer were subsequently deposited on the sapphire substrates by sputtering. The Ti buffer layer was partially oxidized into a TiO2 layer by the O2 gas supply at an elevated temperature. The Ti vapour both from the Ti source powder and the Ti layer pre-deposited on the sapphire substrates is supplied to the solid Au catalysts, forming liquid Au catalysts containing Ti. The interfacial regions between the TiO2 layer and liquid Au catalysts formed by the buffer layer-assisted VLS mechanism, shown in gure 4(c), are in a high-energy state, providing active nucleation sites for TiO2 NWs. TiO2 NWs 4320

Figure 5. PL emission spectra of TiO2 NWs grown on sapphire and quartz substrates, respectively.

having twin structures grow along the [002] direction due to the lattice mismatch between TiO2 (002) and sapphire (0001) planes. One-dimensional growth of bicrystalline NWs shown in gure 4(d) occurs along the entire length with a symmetric twin boundary plane of (101). Figure 5 shows room-temperature photoluminescence (PL) emission spectra of TiO2 NWs prepared using the sapphire and quartz substrates, respectively. TiO2 NWs grown on the quartz substrates clearly show a major PL emission peak at 403 nm (3.08 eV), which almost coincides with the band gap energy (3.0 eV, 415 nm) of the common bulk TiO2 crystals in the rutile structure. PL emission peaks ranging from 450 to 467 nm were also detected and it seems that they are associated with the oxygen vacancies forming at the surface of the TiO2 NWs [12, 16]. These crystalline defects would act as shallowlevel traps and cause the well-known yellow luminescence. However, the intensities of the yellow luminescence are very low and it seems that they do not seriously deteriorate the PL emission properties of TiO2 NWs. The PL emission spectrum from the TiO2 NWs grown on the sapphire substrates shows only one single major peak at 415 nm, which is slightly red shifted compared to that from the TiO2 NWs on quartz. The tensile strain of 3.8084.667% applied to the lattices of TiO2 NWs could cause the energy band gap decrease and thus the red shift in PL emission. These NWs grown on sapphire showed only one single major PL emission without yellow luminescence. Thus, the formation of oxygen vacancies seems almost negligible in these NWs. In the case of NWs grown on quartz as shown in gure 2, they are much longer than those on sapphire, clearly showing the consumption of large amount of Ti from the Ti buffer layer, which is evidenced also by the low-intensity -Ti peak in the XRD patterns, as shown in gure 1. Also, our investigation to the matrix of the NW growth revealed that the surface of quartz substrates is somewhat rough, which also can supply higher Ti vapour pressure than the smooth sapphire substrates. Hence, it is most probable that Ti vapour pressure is higher in the case of the NW growth on quartz and thus Ti content in the NWs could be excess to derive off-stoichiometric TiO2x . Under an excess Ti vapour condition TiO2 NWs could grow on the

Controlled growth of high-quality TiO2 nanowires on sapphire and silica

quartz substrates with a much higher rate compared to those on sapphire substrates. Therefore, the growth of TiO2 NWs having stoichiometric composition would not be achievable under this fast growth condition.

useful for the development of nanoscale optoelectronic and electronic devices by utilizing the well-engineered TiO2 NWs.

Acknowledgment
This study was supported by the Korea Research Foundation (KRF) Grant funded by the Korean Government (MOEHRD) (KRF-2005-041-D00391).

4. Conclusions
Single-crystalline TiO2 NWs were grown on two different substrates of Ti/sapphire (0001) and Ti/quartz using the VLS mechanism. The pre-deposited Ti buffer layer, introduced onto the surface of substrate wafers to prevent the diffusion reactions between Ti vapour and the substrates, promotes the growth of TiO2 NWs. The crystal growth characteristics were investigated and compared for the TiO2 NWs grown on each substrate. TiO2 NWs grown on sapphire substrates showed a twinned structure due to the lattice mismatch between rutile and sapphire, while those on quartz substrates were structurally defect free. The most probable formation mechanism for the twin structure was proposed in this study. The twin structure apparently reveals the strong effect of bottom substrates on the growth of TiO2 NWs despite the existence of the Ti buffer layer at the top. Accordingly, the TiO2 NWs grown on the sapphire substrates show a red shift in PL emission compared to those on the quartz substrates. The TiO2 NWs grown on the quartz substrates show low-intensity yellow luminescence, possibly due to the oxygen vacancies introduced by the excess Ti vapour pressure and the fast NW growth rate. However, the TiO2 NWs grown on quartz substrates showed high-intensity and short-wavelength PL emission. In this study high-quality and size-controlled TiO2 NWs could readily be prepared using both sapphire and quartz substrates. In particular, quartz substrates can provide a great advantage for the fast growth of large scale and high-quality TiO2 NW arrays, which is a very costeffective method of production. This research result may be

References
[1] Andersson M, Osterlund L, Ljungstrom S and Palmqvist A 2002 J. Phys. Chem. B 414 338 [2] Sung Y-M, Lee J-K and Chae W-S 2006 Cryst. Growth Des. 6 805 [3] Sung Y-M and Lee J-K 2004 Cryst. Growth Des. 4 737 [4] Rothschild A, Levakov A, Shapira Y, Ashkenasy N and Komem Y 2003 Surf. Sci. 456 532 [5] Appell D 2002 Nature 419 553 [6] Park N-G, Van de Lagemaat J and Frank A J 2000 J. Phys. Chem. B 104 8989 [7] Miao Z, Xu D, Quyang J, Guo G, Zhao X and Tang Y 2002 Nano Lett. 2 717 [8] Kasuga T, Hiramatsu M, Hoson A, Sekino T and Niihara K 1999 Adv. Mater. 11 1307 [9] Yao B, Chan Y, Zhang X, Zhang W, Yang Z and Wang N 2003 Appl. Phys. Lett. 82 281 [10] Wu J, Shin H, Wu W, Tseng Y and Chen I 2005 J. Cryst. Growth 281 384 [11] Wu J, Wu W and Shih H 2005 J. Electrochem. Soc. 152 G613 [12] Wu J, Shin H and Wu W 2005 J. Vac. Sci. Technol. B 23 2122 [13] Zhang H, Luo X, Xu J, Xiang B and Yu D 2004 J. Phys. Chem. B 108 14866 [14] Wu J, Shin H and Wu W 2006 Nanotechnology 17 105 [15] Tham D, Nam C and Fischer J 2006 Adv. Funct. Mater. 16 1197 [16] Lei Y, Zhang L, Meng G, Li G, Zhang X, Liang C, Chen W and Wang S 2001 Appl. Phys. Lett. 78 1125

4321