The Synthesis of NiO/TiO2 Heterostructures and Their Valence Band Offset Determination
In this work, a heterojunction based on p-type NiO/n-type TiO2 nanostructures has been prepared on the fluorine doped tin oxide (FTO) glass substrate by hydrothermal method. Scanning electron microscopy (SEM) and X-Ray diffraction techniques were used for the morphological and crystalline arrays characterization. The X-ray photoelectron spectroscopy was employed to determine the valence-band offset (VBO) of the NiO/TiO2 heterojunction prepared on FTO glass substrate. The core levels of Ni 2p and Ti 2p were utilized to align the valence-band offset of p-type NiO/n-type TiO2 heterojunction. The valence band offset was found to be ∼0.41 eV and the conduction band was calculated about ∼0.91 eV. The ratio of conduction band offset and the valence-band offset was found to be 2.21.
Recently, the fabrication and the engineering of nanostructures based on metal oxides have drawn effective attention of the researchers due to their specific electronic and optoelectronic features and more practical applications in the industry and technology . Among the various metal oxides, the nanostructures of titanium dioxide (TiO2) are more popular because of their uniqueness and attractive properties in optics, electronics, photochemistry, and biology in addition to its usability in the fabrication of photovoltaic devices [2–4], lithium ion batteries , dye-sensitized solar cells [6, 7], and photocatalysts [8–15]. Different methods have been used to enhance the photocatalysts properties of titanium dioxide such as TiO2-carbon hybrids and doping of TiO2 with metals and nonmetals has also significant contribution on the photocatalysts properties of titanium dioxide nanomaterial [10–12].
Several growth techniques have been used for the synthesis of one dimensional TiO2 nanostructures such as hydrothermal , template synthesis [17, 18], electrochemical etching [19, 20], chemical vapor deposition , and sol-gel process [22, 23]. Among above mentioned methods, the hydrothermal technique is highly promising because of its low temperature, simple, cost effectiveness, and the environment friendly advantages.
Besides titanium dioxide, nickel oxide (NiO) is p-type semiconductor material and is widely used in different applications such as transparent conductive films , electrochromic devices , as a potential candidate in the chemical sensors [26, 27]. NiO exhibits a wide bandgap of 3.6–4.0 eV at room temperature; thus, NiO is considered transparent in the visible light region. Moreover, NiO is largely used as a cocatalyst with different n-type semiconductors due its high p-type concentration, high hole mobility, and low cost . The existence of NiO enhances the separation of electron and hole pairs via electric junction field and also promotes the interfacial charge transfer [29–31]. NiO nanostructures can be synthesized by sputtering , chemical vapor deposition [33, 34], hydrothermal method , and the sol-gel method [35, 36]. The hydrothermal method for the synthesis of NiO nanostructures is relatively more favourable due to its benign features and simplicity.
After surveying the literature it is known that the valence-band offset (VBO) of NiO/ZnO heterojunction has been investigated by few researchers. The growth pattern in their research was as follows: in some cases NiO was used as substrate and ZnO as the epitaxial layer [37, 38]. However in several cases NiO/ZnO based light emitting diodes, ZnO was used as substrate and NiO as the epitaxial layer . The valence-band offset of many heterojunctions determined by XPS is closely linked to the process of growth of heterostructures . To date there is no report about the determination of valence-band offset of NiO/ TiO2 heterostructures.
In the present work, the fabrication and the design of TiO2 and NiO heterostructures are followed by hydrothermal method. Moreover, the valence-band offset (VBO) of NiO/ TiO2 heterojunction is measured by XPS technique. The structural characterization of fabricated heterostructures was determined by scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques.
2. Experimental Section
The growth process of the presented p-n junction based on TiO2 and NiO nanostructures on the fluorine doped tin oxide (FTO) glass substrate by hydrothermal method was as follows. Firstly, a commercially available and cleaned FTO substrate was used for the synthesis of TiO2 and NiO nanostructures. In a typical process 1 mL of TTIP, 20 mL of 37% hydrochloric acid, and 40 mL of deionized water were mixed at constant stirring for 30 minutes. The growth solution was transferred into Teflon vessel of 125 mL capacity and it was sealed in autoclave and kept in preheated oven at 110°C for 12 hours. Afterwards, the TiO2 nanostructures grown FTO substrate was washed with the deionized water and dried at room temperature. NiO nanostructures were grown on the TiO2 nanostructures by hydrothermal method using equimolar concentration of (0.1M) nickel chloride hexahydrate and hexamethylenetetramine and the growth solution was letf at 95°C for 4-6 hours in preheated electric oven. After the completion of growth time, the heterostructures were washed with the deionized water and dried with the flow of nitrogen gas at room temperature. Then heterostructures were annealed at 450°C for the complete conversion of Ni(OH)2 nanostructures into NiO crystalline phase. The structural characterization was performed by scanning electron microscopy and X-ray diffraction and the core levels and valence-band (VB) spectra of the prepared sample were measured by X-ray photoelectron spectrometer (XPS, Thermo ESCALAB 250) using a 1486.6 eV Al Kαsource. All XPS spectra were measured by the C 1 s peak (284.8 eV) as a reference substance in order to compensate the charge effect.
3. Results and Discussion
3.1. The Structural Characterization of p-Type NiO/n-Type TiO2 Heterostructures
A typical SEM image of TiO2 nanostructures grown on FTO glass substrate by hydrothermal growth technique is shown in Figure 1(a). It can be seen that nanostructures are dense and perpendicular to the substrate. The average diameter and length of nanostructures are 100 nm and 500 nm, respectively. Figure 1(b) shows the SEM image of NiO nanostructures and it can be observed that the nanostructures are like a porous structure. Figure 1(c) shows the composite structures of NiO/ TiO2 nanostructures and from the presented image it is clear that almost top surface of TiO2 nanostructures is fully covered with the nanostructures of NiO.
Figure 1(d) shows the diffraction pattern of NiO/ TiO2 nanostructures grown on the FTO glass substrate at room temperature. All the diffraction peaks could be assigned to rutile phase of TiO2 and well match to the JCPDS (card number 211276). The intense (002) peak reflects that the preferred orientation of TiO2 nanorods is along the (001) direction. However, some peaks of NiO are also shown in Figure 1(d) and it can be seen that the sample is composed of NiO and TiO2 nanostructures. Some diffraction peaks also appeared for FTO glass substrates which are indicated by star sign.
3.2. The Calculation of Band Offset by XPS Measurement
Figure 2 shows the core level (CL) spectrum of spin-orbit splitting of Ti 2p and Ni 2p peaks. The CL spectrum of Ni 2p 3/2 is represented by Figure 2(a) and two dominant peaks are found at 854.13 eV and 855.78 eV which are mainly concerned the Ni–O linkages. Figure 2(b) shows that the Ti 2p 3/2 peak at eV is indexed to the Ti–O bond and the peak at eV is assigned to the Ti 2p oxidation state [41–43]. Both measured both peaks are symmetric and the FWHM of Ti 2p 3/2 is found to be 1.1 eV that is matching with the reported values, and it is attributed to the defect free TiO2 synthesized by sol-gel method (110) [42, 43]. The nickel 2p and Ti 2p peaks in the NiO/ TiO2 heterostructures are shown in Figures 2(c) and 2(d). It has been indicated that the measured peaks are symmetric relative to that of information obtained from the pure samples of NiO and TiO2, the change in Ni 2p peak is observed from the value 0.3 eV to the binding energy value of 853.839 eV and the Ti 2p 3/2 is changed from the 0.056 to 459.16 eV. The valence-band (VB) spectrum of NiO and TiO2 is shown in Figures 3(a) and 3(b). The valence-band maximum (VBM) value of 0.73 eV for NiO is extrapolated from the VB spectrum using linear fitting. The VB spectrum for TiO2 was measured by similar a method as for NiO and is shown in Figure 3(b) and the VBM value of 0.73 eV was observed. For O 1 s in the NiO sample, the less intense peak at a binding energy of 529.47 eV corresponds to the O 1 s peak of NiO. The very intense shoulder peak at 533.3 eV is assigned to the surface adsorbed oxygen as shown in Figure 3(c). The O 1 s spectrum of Ti–O is comprised on the two apparent peaks, one at 530.48 eV is attributed to the Ti–O bonds and the other at 532.21 eV because of the surface adsorbed species as shown in Figure 3(d). The reported method  was used for the measurement of valence-band offset of NiO/TiO2 heterojunctions by applying the following formula:
Here is the energy difference between Ni 2p and VBM in the pure NiO nanostructures, ( is the energy difference between the Ti 2p and the VBM in the TiO2, and is the energy difference between the Ti 2p and Ni 2p core levels (CLs) in the NiO/ TiO2 heterostructures. Hence the measured valance-band offset of developed heterojunction is found to be ~0.41 eV. The conduction-band offset of NiO/ TiO2 heterojunction was measured by the following formula:
The respective band gap for the NiO is 3.7 eV and 3.2 eV for TiO2, respectively, at room temperature; thus the calculated is found to be ~0.91 eV. However the schematic diagram of the band alignment is depicted in Figure 4. It can be observed that a type-II band alignment is produced at the junction of NiO/ TiO2 heterojunction. The observed ratio of CBO and VBO / is 2.21.
In this study, the hydrothermal approach was used for the development of p-type NiO/n-type TiO2 heterojunction on the FTO glass substrate. The SEM and XRD techniques were used for the morphological and structural characterization. The XPS technique was used for the measurement of valence-band offset and the observed band offset was found to be ~0.41 eV and the conduction band of ~0.91 eV was determined. The ratio of conduction band and valence-band offset was found to be 2.21.
Conflict of Interests
The authors declare that there is no conflict of interests regarding the publication of this paper.
This project was supported by King Saud University, Deanship of Scientific Research, and College of Science Research Centre.
G. R. Patzke, F. Krumeich, and R. Nesper, “Oxidic nanotubes and nanorods anisotropic modules for a future nanotechnology,” Angewandte Chemie—International Edition, vol. 41, no. 14, pp. 2446–2461, 2002.View at: Publisher Site | Google Scholar
M. Grätzel, “Sol-gel processed TiO2 films for photovoltaic applications,” Journal of Sol-Gel Science and Technology, vol. 22, no. 1-2, pp. 7–13, 2001.View at: Publisher Site | Google Scholar
Z. X. Ge, A. X. Wei, J. Liu, W. Zhao, and C. B. Liu, “Synthesis and photovoltaic devices performance of single crystalline TiO2 nanowire bundle arrays,” Journal of Inorganic Materials, vol. 25, no. 10, pp. 1105–1109, 2010.View at: Publisher Site | Google Scholar
H. Chen, W. Y. Fu, H. B. Yang et al., “Photosensitization of TiO2 nanorods with CdS quantum dots for photovoltaic devices,” Electrochimica Acta, vol. 56, no. 2, pp. 919–924, 2010.View at: Publisher Site | Google Scholar
Y. K. Zhou, L. Cao, F. B. Zhang, B. L. He, and H. L. Li, “Lithium insertion into TiO2 nanotube prepared by the hydrothermal process,” Journal of the Electrochemical Society, vol. 150, no. 9, pp. A1246–A1249, 2003.View at: Publisher Site | Google Scholar
P. Charoensirithavorn, Y. Ogomi, T. Sagawa, S. Hayase, and S. Yoshikawa, “A facile route to TiO2 nanotube arrays for dye-sensitized solar cells,” Journal of Crystal Growth, vol. 311, no. 3, pp. 757–759, 2009.View at: Publisher Site | Google Scholar
M. Anpo, “Preparation, characterization, and reactivities of highly functional titanium oxide-based photocatalysts able to operate under UV-visible light irradiation: approaches in realizing high efficiency in the use of visible light,” Bulletin of the Chemical Society of Japan, vol. 77, no. 8, pp. 1427–1442, 2004.View at: Publisher Site | Google Scholar
B. Q. Su, Y. J. Ma, Y. L. Du, C. Yang, and C. M. Wang, “In situ photoelectrocatalytic degradation behavior of methylene blue on Nano-TiO2 modified electrode,” Journal of the Electrochemical Society, vol. 155, no. 10, pp. F213–F217, 2008.View at: Publisher Site | Google Scholar
Y. Xie, “Photoelectrochemical application of nanotubular titania photoanode,” Electrochimica Acta, vol. 51, no. 17, pp. 3399–3406, 2006.View at: Publisher Site | Google Scholar
G. Yan, M. Zhang, J. Hou, and J. Yang, “Photoelectrochemical and photocatalytic properties of N+S co-doped TiO2 nanotube array films under visible light irradiation,” Materials Chemistry and Physics, vol. 129, no. 1-2, pp. 553–557, 2011.View at: Publisher Site | Google Scholar
M. Zhang, J. Wu, J. Hou, and J. Yang, “Molybdenum and nitrogen co-doped titanium dioxide nanotube arrays with enhanced visible light photocatalytic activity,” Science of Advanced Materials, vol. 5, no. 6, pp. 535–541, 2013.View at: Publisher Site | Google Scholar
M. Zhang, J. Wu, D. Lu, and J. Yang, “Enhanced visible light photocatalytic activity for TiO2 nanotube array films by codoping with tungsten and nitrogen,” International Journal of Photoenergy, vol. 2013, Article ID 471674, 8 pages, 2013.View at: Publisher Site | Google Scholar
R. Ciancio, E. Carlino, C. Aruta, D. MacCariello, F. M. Granozio, and U. S. Di Uccio, “Nanostructure of buried interface layers in TiO2 anatase thin films grown on LaAlO3 and SrTiO3 substrates,” Nanoscale, vol. 4, no. 1, pp. 91–94, 2012.View at: Publisher Site | Google Scholar
S. Guo, S. Han, H. Mao et al., “Synthesis and characterization of nitrogen and phosphate codoped titanium dioxide with excellent visible-light photocatalytic activity,” Journal of Alloys and Compounds, vol. 544, pp. 50–54, 2012.View at: Publisher Site | Google Scholar
I. Lee, J. B. Joo, Y. Yin, and F. Zaera, “A [email protected] nanoarchitecture for Au/TiO2 catalysts,” Angewandte Chemie—International Edition, vol. 50, no. 43, pp. 10208–10211, 2011.View at: Publisher Site | Google Scholar
Y. P. Guo, N. H. Lee, H. J. Oh et al., “Preparation of titanate nanotube thin film using hydrothermal method,” Thin Solid Films, vol. 516, no. 23, pp. 8363–8371, 2008.View at: Publisher Site | Google Scholar
C. Suwanchawalit and S. Wongnawa, “Triblock copolymer-templated synthesis of porous TiO2 and its photocatalytic activity,” Journal of Nanoparticle Research, vol. 12, no. 8, pp. 2895–2906, 2010.View at: Publisher Site | Google Scholar
A. Michailowski, D. Almawlawi, G. S. Cheng, and M. Moskovits, “Highly regular anatase nanotubule arrays fabricated in porous anodic templates,” Chemical Physics Letters, vol. 349, no. 1-2, pp. 1–5, 2001.View at: Publisher Site | Google Scholar
Y. S. Tian, C. G. Hu, X. S. He, C. L. Cao, G. S. Huang, and K. Y. Zhang, “Titania nanotube arrays for light sensor and UV photometer,” Sensors and Actuators B, vol. 144, no. 1, pp. 203–207, 2010.View at: Publisher Site | Google Scholar
P. Xiao, D. Liu, B. B. Garcia, S. Sepehri, Y. Zhang, and G. Cao, “Electrochemical and photoelectrical properties of titania nanotube arrays annealed in different gases,” Sensors and Actuators B, vol. 134, no. 2, pp. 367–372, 2008.View at: Publisher Site | Google Scholar
W. Li, S. I. Shah, C. P. Huang, O. Jung, and C. Ni, “Metallorganic chemical vapor deposition and characterization of TiO2 nanoparticles,” Materials Science and Engineering B, vol. 96, no. 3, pp. 247–253, 2002.View at: Publisher Site | Google Scholar
B. Mukherjee, C. Karthik, and N. Ravishankar, “Hybrid sol-gel combustion synthesis of nanoporous anatase,” Journal of Physical Chemistry C, vol. 113, no. 42, pp. 18204–18211, 2009.View at: Publisher Site | Google Scholar
K. Kanie and T. Sugimoto, “Shape control of anatase TiO2 nanoparticles by amino acids in a gel-sol system,” Chemical Communications, no. 14, pp. 1584–1585, 2004.View at: Google Scholar
H. Sato, T. Minami, S. Takata, and T. Yamada, “Transparent conducting p-type NiO thin films prepared by magnetron sputtering,” Thin Solid Films, vol. 236, no. 1-2, pp. 27–31, 1993.View at: Google Scholar
X. C. Lou, X. J. Zhao, and X. He, “Boron doping effects in electrochromic properties of NiO films prepared by sol-gel,” Solar Energy, vol. 83, no. 12, pp. 2103–2108, 2009.View at: Publisher Site | Google Scholar
H. Steinebach, S. Kannan, L. Rieth, and F. Solzbacher, “H2 gas sensor performance of NiO at high temperatures in gas mixtures,” Sensors and Actuators B, vol. 151, no. 1, pp. 162–168, 2010.View at: Publisher Site | Google Scholar
M. A. Abbasi, Z. H. Ibupoto, M. Hussain et al., “Potentiometric zinc ion sensor based on honeycomb-like NiO nanostructures,” Sensors, vol. 12, no. 11, pp. 15424–15437, 2012.View at: Publisher Site | Google Scholar
Z. Zhang, C. Shao, X. Li, C. Wang, M. Zhang, and Y. Liu, “Electrospun nanofibers of p-type NiO/n-type ZnO heterojunctions with enhanced photocatalytic activity,” ACS Applied Materials and Interfaces, vol. 2, no. 10, pp. 2915–2923, 2010.View at: Publisher Site | Google Scholar
C. Shifu, Z. Sujuan, L. Wei, and Z. Wei, “Preparation and activity evaluation of p-n junction photocatalyst NiO/TiO2,” Journal of Hazardous Materials, vol. 155, no. 1-2, pp. 320–326, 2008.View at: Publisher Site | Google Scholar
Y. Ku, C. N. Lin, and W. M. Hou, “Characterization of coupled NiO/TiO2 photocatalyst for the photocatalytic reduction of Cr(VI) in aqueous solution,” Journal of Molecular Catalysis A, vol. 349, no. 1-2, pp. 20–27, 2011.View at: Publisher Site | Google Scholar
Y. Chen, J. C. Crittenden, S. Hackney, L. Sutter, and D. W. Hand, “Preparation of a novel TiO2-based p-n junction nanotube photocatalyst,” Environmental Science and Technology, vol. 39, no. 5, pp. 1201–1208, 2005.View at: Publisher Site | Google Scholar
J. L. Chung, J. C. Chen, and C. J. Tseng, “Preparation of TiO2-doped ZnO films by radio frequency magnetron sputtering in ambient hydrogen-argon gas,” Applied Surface Science, vol. 255, no. 5, pp. 2494–2499, 2008.View at: Publisher Site | Google Scholar
J. K. Kang and S. W. Rhee, “Chemical vapor deposition of nickel oxide films from Ni(C5H5)2/O2,” Thin Solid Films, vol. 391, no. 1, pp. 57–61, 2001.View at: Publisher Site | Google Scholar
K. Zheng, L. Gu, D. Sun, X. Mo, and G. Chen, “The properties of ethanol gas sensor based on Ti doped ZnO nanotetrapods,” Materials Science and Engineering B, vol. 166, no. 1, pp. 104–107, 2010.View at: Publisher Site | Google Scholar
B. A. Reguig, A. Khelil, L. Cattin, M. Morsli, and J. C. Bernède, “Properties of NiO thin films deposited by intermittent spray pyrolysis process,” Applied Surface Science, vol. 253, no. 9, pp. 4330–4334, 2007.View at: Publisher Site | Google Scholar
R. G. S. Pala, W. Tang, M. M. Sushchikh et al., “CO oxidation by Ti- and Al-doped ZnO: oxygen activation by adsorption on the dopant,” Journal of Catalysis, vol. 266, no. 1, pp. 50–58, 2009.View at: Publisher Site | Google Scholar
R. Deng, B. Yao, Y. F. Li et al., “X-ray photoelectron spectroscopy measurement of n-ZnO/p-NiO heterostructure valence-band offset,” Applied Physics Letters, vol. 94, no. 2, Article ID 022108, 2009.View at: Publisher Site | Google Scholar
Y. Ishida, A. Fujimori, H. Ohta, M. Hirano, and H. Hosono, “Potential profiling of the nanometer-scale charge-depletion layer in n-ZnO/p-NiO junction using photoemission spectroscopy,” Applied Physics Letters, vol. 89, no. 15, Article ID 153502, 2006.View at: Publisher Site | Google Scholar
H. Long, G. J. Fang, H. H. Huang et al., “Ultraviolet electroluminescence from ZnO/NiO-based heterojunction light-emitting diodes,” Applied Physics Letters, vol. 95, no. 1, Article ID 013509, 2009.View at: Publisher Site | Google Scholar
P. Zurcher and R. S. Bauer, “Photoemission determination of dipole layer and VB‐discontinuity formation during the MBE growth of GaAs on Ge(110),” Journal of Vacuum Science and Technology A, vol. 1, no. 2, pp. 695–700, 1982.View at: Publisher Site | Google Scholar
W. Göpel, J. A. Anderson, D. Frankel et al., “Surface defects of TiO2(110): a combined XPS, XAES AND ELS study,” Surface Science, vol. 139, no. 2-3, pp. 333–346, 1984.View at: Google Scholar
S. Pétigny, H. Mostéfa-Sba, B. Domenichini, E. Lesniewska, A. Steinbrunn, and S. Bourgeois, “Superficial defects induced by argon and oxygen bombardments on (110) TiO2 surfaces,” Surface Science, vol. 410, no. 2-3, pp. 250–257, 1998.View at: Google Scholar
S. A. Bilmes, P. Mandelbaum, F. Alvarez, and N. M. Victoria, “Surface and electronic structure of titanium dioxide photocatalysts,” Journal of Physical Chemistry B, vol. 104, no. 42, pp. 9851–9858, 2000.View at: Google Scholar
S. H. Wei and A. Zunger, “Calculated natural band offsets of all II–VI and III–V semiconductors: chemical trends and the role of cation d orbitals,” Applied Physics Letters, vol. 72, no. 16, pp. 2011–2013, 1998.View at: Publisher Site | Google Scholar