Enhanced Electron Transport in Epitaxial Annealed Graphene Titanium Dioxide Heterojunction
Abstract
Titanium dioxide (TiO2) photocatalyst is a widely acceptable photo catalyst candidate due to its environment friendliness, cost-effectiveness, intrinsic electronics, photostability, good surface properties, and non-toxicity. However, TiO2 faces significant challenges for commercial exploitations, including high recombination rates, low quantum yield, and low visible light photo conversion efficiency. In this research, the optical properties of graphene TiO2 heterojunction were evaluated in measurements of Transmittance and Reflectance. Optical parameters in terms of WDD dispersion energy and dielectric constants were studied by annealing the films in the air up to 450 °C at 1 step, 2 °C/min and 1 °C/min annealing rates. Transmittance for the film annealed at 1 °C/min showed the highest transmittance of 86.57% and 74.07% for graphene and graphene TiO2, respectively. SCOUT software modelled Transmittance data to obtain refractive index. Refractive indices for pristine, 1 step, 2 °C/min, and 1 °C/min TiO2 films obtained at 550 nm were found to be 0.51, 034, 0.40 and 0.49, respectively. Porosity and dispersion energy for the lowest annealing rates (1 oC/min) was found to be 49 % and 12.7 eV in that order. Real and imaginary Interband transition (2.33–4.04) x 10-6 and (0.23–2.73) x 10-6 in that order, linear and nonlinear optical susceptibility (1.42–2.18) x 10-1 and (4.12–22.50) x 10-14, optical conductivity (2.51–13.2) x 1013 and electrical conductivity (3.89–4.60) x 1010 were enhanced with decreasing annealing rates. This is due to pole filing, film densification, increased lattice absorption and scattering centres and improved crystallinity of the films due to heat treatment and large-area graphene anchoring. The findings revealed that annealing graphene - TiO2 passivates its surface, reducing its boundary traps owing to quantum confinement effects and improving the electron transport throughout the heterojunction.
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Serrano, E., Rus, G., & García-Martínez, J. (2009). Nanotechnology for sustainable energy. Renewable and Sustainable Energy Reviews, 13(9), 2373–2384. doi: 10.1016/j.rser.2009.06.003
Drunka, R., Grabis, J., Jankovica, D., Krumina, A., & Rasmane, D. (2015). Microwave-assisted synthesis and photocatalytic properties of sulphur and platinum modified TiO2nanofibers. IOP Conference Series: Materials Science and Engineering, 77, 012010. doi: 10.1088/1757-899x/77/1/012010
Wang, S., Pan, L., Song, J.-J., Mi, W., Zou, J.-J., Wang, L., & Zhang, X. (2015). Titanium-Defected Undoped Anatase TiO2 with p-Type Conductivity, Room-Temperature Ferromagnetism, and Remarkable Photocatalytic Performance. Journal of the American Chemical Society, 137(8), 2975–2983. doi: 10.1021/ja512047k
Singh, R. (2004). Nano-structured CdTe, CdS and TiO2 for thin film solar cell applications. Solar Energy Materials and Solar Cells, 82(1–2), 315–330. doi: 10.1016/j.solmat.2004.02.006
Zallen, R., & Moret, M. P. (2006). The optical absorption edge of brookite TiO2. Solid State Communications, 137(3), 154–157. doi: 10.1016/j.ssc.2005.10.024
Matthews, R. W. (1987). Photooxidation of organic impurities in water using thin films of titanium dioxide. The Journal of Physical Chemistry, 91(12), 3328–3333. doi: 10.1021/j100296a044
Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K., & Taga, Y. (2001). Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides. Science, 293(5528), 269–271. doi: 10.1126/science.1061051
Hu, G., & Tang, B. (2013). Photocatalytic mechanism of graphene/titanate nanotubes photocatalyst under visible-light irradiation. Materials Chemistry and Physics, 138(2–3), 608–614. doi: 10.1016/j.matchemphys.2012.12.027
Qianqian, Z., Tang, B., & Guoxin, H. (2011). High photoactive and visible-light responsive graphene/titanate nanotubes photocatalysts: Preparation and characterization. Journal of Hazardous Materials, 198, 78–86. doi: 10.1016/j.jhazmat.2011.10.012
Hasan, M. M., Haseeb, A. S. M. A., Saidur, R., Masjuki, H. H., & Hamdi, M. (2009). Synthesis and Annealing of Nanostructured TiO2 Films by Radio-Frequency Magnetron Sputtering. Journal of Applied Sciences, 9(15), 2815–2821. doi: 10.3923/jas.2009.2815.2821
Gu, Y., Xing, M., & Zhang, J. (2014). Synthesis and photocatalytic activity of graphene based doped TiO2 nanocomposites. Applied Surface Science, 319, 8–15. doi: 10.1016/j.apsusc.2014.04.182
Cai, J., Wu, X., Li, S., & Zheng, F. (2017). Controllable location of Au nanoparticles as cocatalyst onto TiO2@CeO2 nanocomposite hollow spheres for enhancing photocatalytic activity. Applied Catalysis B: Environmental, 201, 12–21. doi: 10.1016/j.apcatb.2016.08.003
Cheng, L., Qiu, S., Chen, J., Shao, J., & Cao, S. (2017). A practical pathway for the preparation of Fe2O3 decorated TiO2 photocatalyst with enhanced visible-light photoactivity. Materials Chemistry and Physics, 190, 53–61. doi: 10.1016/j.matchemphys.2017.01.001
Qi, K., Selvaraj, R., Al Fahdi, T., Al-Kindy, S., Kim, Y., Wang, G.-C., Tai, C.-W., & Sillanpää, M. (2016). Enhanced photocatalytic activity of anatase-TiO2 nanoparticles by fullerene modification: A theoretical and experimental study. Applied Surface Science, 387, 750–758. doi: 10.1016/j.apsusc.2016.06.134
Qin, X., He, F., Chen, L., Meng, Y., Liu, J., Zhao, N., & Huang, Y. (2016). Oxygen-vacancy modified TiO2 nanoparticles as enhanced visible-light driven photocatalysts by wrapping and chemically bonding with graphite-like carbon. RSC Advances, 6(13), 10887–10894. doi: 10.1039/c5ra27209b
Rahbar, M., & Behpour, M. (2016). Multi-walled carbon nanotubes/TiO2 thin layer for photocatalytic degradation of organic pollutant under visible light irradiation. Journal of Materials Science: Materials in Electronics, 27(8), 8348–8355. doi: 10.1007/s10854-016-4845-2
Tang, B., Chen, H., Peng, H., Wang, Z., & Huang, W. (2018). Graphene Modified TiO2 Composite Photocatalysts: Mechanism, Progress and Perspective. Nanomaterials, 8(2), 105. doi: 10.3390/nano8020105
Novoselov, K. S., Geim, A. K., Morozov, S. V., Jiang, D., Katsnelson, M. I., Grigorieva, I. V., Dubonos, S. V., & Firsov, A. A. (2005). Two-dimensional gas of massless Dirac fermions in graphene. Nature, 438(7065), 197–200. doi: 10.1038/nature04233
Balandin, A. A., Ghosh, S., Bao, W., Calizo, I., Teweldebrhan, D., Miao, F., & Lau, C. N. (2008). Superior Thermal Conductivity of Single-Layer Graphene. Nano Letters, 8(3), 902–907. doi: 10.1021/nl0731872
Balandin, A. A., Ghosh, S., Bao, W., Calizo, I., Teweldebrhan, D., Miao, F., & Lau, C. N. (2008). Superior Thermal Conductivity of Single-Layer Graphene. Nano Letters, 8(3), 902–907. doi: 10.1021/nl0731872
WTheiss Hardware and Software. (2023). Scout. Retrieved from https://wtheiss.com/wordpress/?cat=4
Kazmi, S. A., Hameed, S., Ahmed, A. S., Arshad, Mohd., & Azam, A. (2017). Electrical and optical properties of graphene-TiO2 nanocomposite and its applications in dye sensitized solar cells (DSSC). Journal of Alloys and Compounds, 691, 659–665. doi: 10.1016/j.jallcom.2016.08.319
Frederichi, D., Scaliante, M. H. N. O., & Bergamasco, R. (2020). Structured photocatalytic systems: photocatalytic coatings on low-cost structures for treatment of water contaminated with micropollutants—a short review. Environmental Science and Pollution Research, 28(19), 23610–23633. doi: 10.1007/s11356-020-10022-9
John, B. M. , Mugo, S. W. , & Ngaruiya, J. M. (2018). Effect of Annealing Rates on Surface Roughness of TiO2 Thin films. Journal of Materials Physics and Chemistry, 6(2), 43-46.
Gupta, V., & Mansingh, A. (1996). Influence of postdeposition annealing on the structural and optical properties of sputtered zinc oxide film. Journal of Applied Physics, 80(2), 1063–1073. doi: 10.1063/1.362842
Abeles, F. (1972). Optical Properties of Solids. London: North-Holland Publishing Company.
Hassanien, A. S., & Akl, A. A. (2018). Optical characteristics of iron oxide thin films prepared by spray pyrolysis technique at different substrate temperatures. Applied Physics A, 124(11). doi: 10.1007/s00339-018-2180-6
Ye, Q., Liu, P. Y., Tang, Z. F., & Zhai, L. (2007). Hydrophilic properties of nano-TiO2 thin films deposited by RF magnetron sputtering. Vacuum, 81(5), 627–631. doi: 10.1016/j.vacuum.2006.09.001
Liu, J., Gan, D., Hu, C., Kiene, M., Ho, P. S., Volksen, W., & Miller, R. D. (2002). Porosity effect on the dielectric constant and thermomechanical properties of organosilicate films. Applied Physics Letters, 81(22), 4180–4182. doi: 10.1063/1.1525054
Bouvard, D., & Lange, F. F. (1992). Correlation between random dense parking and random dense packing for determining particle coordination number in binary systems. Physical Review A, 45(8), 5690–5693. doi: 10.1103/physreva.45.5690
Ni, M., Leung, M. K. H., Leung, D. Y. C., & Sumathy, K. (2006). An analytical study of the porosity effect on dye-sensitized solar cell performance. Solar Energy Materials and Solar Cells, 90(9), 1331–1344. doi: 10.1016/j.solmat.2005.08.006
Ohyama, M., Kouzuka, H., & Yoko, T. (1997). Sol-gel preparation of ZnO films with extremely preferred orientation along (002) plane from zinc acetate solution. Thin Solid Films, 306(1), 78–85. doi: 10.1016/s0040-6090(97)00231-9
Smestad, G. P., Spiekermann, S., Kowalik, J., Grant, C. D., Schwartzberg, A. M., Zhang, J., Tolbert, L. M., & Moons, E. (2003). A technique to compare polythiophene solid-state dye sensitized TiO2 solar cells to liquid junction devices. Solar Energy Materials and Solar Cells, 76(1), 85–105. doi: 10.1016/s0927-0248(02)00252-0
Wemple, S. H., & DiDomenico, M. (1969). Oxygen‐Octahedra Ferroelectrics. II. Electro‐optical and Nonlinear‐Optical Device Applications. Journal of Applied Physics, 40(2), 735–752. doi: 10.1063/1.1657459
Wemple, S. H., & DiDomenico, M. (1971). Behavior of the Electronic Dielectric Constant in Covalent and Ionic Materials. Physical Review B, 3(4), 1338–1351. doi: 10.1103/physrevb.3.1338
Tan, W. C., Koughia, K., Singh, J., & Kasap, S. O. (2006). Fundamental Optical Properties of Materials I. Optical Properties of Condensed Matter and Applications, 1–25. doi: 10.1002/0470021942.ch1
Márquez, E., Ramírez-malo, J. B., Villares, P., Jiménez-Garay, R., & Swanepoel, R. (1995). Optical characterization of wedge-shaped thin films of amorphous arsenic trisulphide based only on their shrunk transmission spectra. Thin Solid Films, 254(1–2), 83–91. doi: 10.1016/0040-6090(94)06267-o
Wagner, S. J., Meier, J., Helmy, A., Stewart, A., Sorel, M., & Hutchings, D. (2007). Polarization-dependent nonlinear refraction and two-photon absorption in GaAs/AlAs superlattice waveguides below the half-bandgap. Journal of the Optical Society of America B, 24, 1557-1563.
Hassanien, A. S., Sharma, I., & Akl, A. A. (2020). Physical and optical properties of a-Ge-Sb-Se-Te bulk and film samples: Refractive index and its association with electronic polarizability of thermally evaporated a-Ge15-xSbxSe50Te35 thin-films. Journal of Non-Crystalline Solids, 531, 119853. doi: 10.1016/j.jnoncrysol.2019.119853
Spicer, W. E. (1972). Introduction. In F. Abeles (Ed.), Optical Properties of Solids. London: North-Holland Publishing Company.
Chander, S., & Dhaka, M. S. (2016). Thermal evolution of physical properties of vacuum evaporated polycrystalline CdTe thin films for solar cells. Journal of Materials Science: Materials in Electronics, 27(11), 11961–11973. doi: 10.1007/s10854-016-5343-2
Astinchap, B., Moradian, R., & Gholami, K. (2017). Effect of sputtering power on optical properties of prepared TiO 2 thin films by thermal oxidation of sputtered Ti layers. Materials Science in Semiconductor Processing, 63, 169–175. doi: 10.1016/j.mssp.2017.02.007
Yang, C., Fan, H., Xi, Y., Chen, J., & Li, Z. (2008). Effects of depositing temperatures on structure and optical properties of TiO2 film deposited by ion beam assisted electron beam evaporation. Applied Surface Science, 254(9), 2685–2689. doi: 10.1016/j.apsusc.2007.10.006
Loughin, S., French, R. H., Noyer, L. K. D., Ching, W.-Y., & Xu, Y.-N. (1996). Critical point analysis of the interband transition strength of electrons. Journal of Physics D: Applied Physics, 29(7), 1740–1750. doi: 10.1088/0022-3727/29/7/009
Al-Mudhaffer, M. F., Nattiq, M. A., Jaber, M. A. (2012). Linear optical properties and energy loss function of Novolac: Epoxy blend film. Archive Applied Science Research, 4(4), 1731–1740.
Yakuphanoglu, F., Cukurovali, A., & Yilmaz, İ. (2004). Single-oscillator model and determination of optical constants of some optical thin film materials. Physica B: Condensed Matter, 353(3–4), 210–216. doi: 10.1016/j.physb.2004.09.097
Sarkar, S., Garain, S., Mandal, D., & Chattopadhyay, K. K. (2014). Electro-active phase formation in PVDF–BiVO4 flexible nanocomposite films for high energy density storage application. RSC Adv., 4(89), 48220–48227. doi: 10.1039/c4ra08427f
Crane, M., & Hassan, Y. (1989). Solar Cells (Collage of Education, University of Mosul). N. d.
Nowotny, J., Sorrell, C. C., Bak, T., & Sheppard, L. R. (2005). Defect disorder, transport and photoelectrochemical properties of TiO 2. Materials for Energy Conversion Devices, 84–119. doi: 10.1533/9781845690915.1.84
Yakuphanoglu, F., Cukurovali, A., & Yilmaz, İ. (2005). Refractive index and optical absorption properties of the complexes of a cyclobutane containing thiazolyl hydrazone ligand. Optical Materials, 27(8), 1363–1368. doi: 10.1016/j.optmat.2004.09.021
Mugambi, N., Mbiyu Ngaruiya, J., Waweru Mugo, S., Gitonga Riungu, G., & Mbae John, G. (2021). Influence of Post Annealing Rates on Porosity, Dispersion Energy and Associated Dielectric Energy Losses of TiO2 Thin Films. Journal of Photonic Materials and Technology, 7(1), 1. doi: 10.11648/j.jmpt.20210701.11
Aljufairi, N. H. (2012). Electric properties and surface structure of TiO2 for solar cells. Energy, 39(1), 6–10. doi: 10.1016/j.energy.2011.08.057Article Metrics
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