Advanced
Titanium Dioxide Sol-gel Schottky Diodes and Effect of Titanium Dioxide Nanoparticle
Titanium Dioxide Sol-gel Schottky Diodes and Effect of Titanium Dioxide Nanoparticle
Journal of Electrical Engineering and Technology. 2015. Nov, 10(6): 2343-2347
Copyright © 2015, The Korean Institute of Electrical Engineers
This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/3.0/) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
  • Received : January 15, 2015
  • Accepted : May 24, 2015
  • Published : November 01, 2015
Download
PDF
e-PUB
PubReader
PPT
Export by style
Article
Author
Metrics
Cited by
TagCloud
About the Authors
Mohammad Maniruzzaman
Dept. of Mech. Eng., Inha University, Korea. (mamun08me@yahoo.com,duicaofei@naver.com,bobtf@daum.net)
Lindong Zhai
Dept. of Mech. Eng., Inha University, Korea. (mamun08me@yahoo.com,duicaofei@naver.com,bobtf@daum.net)
Seongcheol Mun
Dept. of Mech. Eng., Inha University, Korea. (mamun08me@yahoo.com,duicaofei@naver.com,bobtf@daum.net)
Jaehwan Kim
Corresponding Author: Dept. of Mech. Eng., Inha University, Korea. (jaehwan@inha.ac.kr)

Abstract
This paper reports the effect of Titanium dioxide (TiO 2 ) nanoparticles on a TiO 2 sol-gel Schottky diode. TiO 2 nanoparticles were blended with TiO 2 sol-gel to fabricate the Schottky diode. TiO 2 nanoparticles showed strong anatase and rutile X-ray diffraction peaks. However, the mixture of TiO 2 sol-gel and TiO 2 nanoparticles exhibited no anatase and rutile peaks. The forward current of the Schottky diode drastically increased as the concentration of TiO 2 nanoparticles increased up to 10 wt. % and decreased after that. The possible conduction mechanism is more likely space charge limited conduction.
Keywords
1. Introduction
Recently metal oxides have attracted great attention due to their remarkable optical, physical, chemical, and electronic properties [1 , 2] . Among the metal oxides, titanium oxide (TiO 2 ) has a wide range of advantageous properties, such as chemical stability, photocatalytic activity, photosensitivity, and electrical conductivity and is applicable to electronic devices, chemical sensors, photocatalysts, solar cells, and photoelectrochemical cells [3 - 6] . These properties strongly depend on crystallite size and shape of the TiO 2 . TiO 2 has three main crystalline structures including anatase, rutile and brookite. Each structure has unique chemical, physical, and electronic properties and leads different applications.
TiO 2 thin films have been fabricated with a variety of techniques including sol-gel process, sputtering with different metallic and ceramic targets, ion beam enhanced deposition, chemical vapor deposition, and pulsed laser deposition. Sol-gel process is one of the most important techniques to synthesize various functional materials. It has advantages over conventional other techniques in terms of low temperature process, large area coating, homogeneous and multi-component metal oxide preparation and low equipment cost. Although sol-gel process has such a superior advantages, the final material performance is greatly affected by the process conditions including species of solvent, concentration of TiO 2 and heating process.
In this paper, we report the fabrication of a Schottky diode made by mixing TiO 2 nanoparticles and TiO 2 solgel. Schottky diodes have been made with inorganic semiconducting material, conducting polymers and a combination of both materials [7 - 10] . The effect of TiO 2 nanoparticles in the TiO 2 sol-gel for the performance of Schottky diode is investigated in terms of surface field emission scanning electron microscope (FESEM) images, x-ray diffraction (XRD) patterns and current-voltage (I-V) characteristics of the fabricated Schottky diode. Three possible conduction mechanisms are explained to determine dominant conduction process in the device.
2. Experimental procedure
TiO 2 nanoparticles (~30 nm) were purchased from Aldrich Co. and used without further purification. The TiO 2 sol was fabricated by titanium (IV) isopropoxide (TIP, 97 %), ethanol (99.8 %), HCl (36.4 %) and deionized (DI) water. The sol was prepared as follows: 50 ml of ethanol was charged in the 100 ml of round bottom flask, and 6 g of TIP was added to the solution. Then, HCl was added to the mixture until the solution became transparent with stirring, and the solution was kept under vigorous stirring for 1 day. The aqueous TiO 2 nanoparticle solution was directly mixed with TiO 2 sol-solution with 1 wt% (TiO-1), 5 wt% (TiO-5), 10 wt% (TiO-10), and 15 wt% (TiO-15) TiO 2 nanoparticle concentrations. The various concentrations of TiO 2 nanoparticles and TiO 2 sol mixtures were spin coated on a silicon wafer with 2000 rpm. The film was then heated at 300℃ for 1 h in a tube furnace under nitrogen gas purging. The silicon wafer was cleaned by a mixture of sulfuric acid and hydrogen peroxide in an ultrasonic cleaner, followed by cleaning and rinsing with de-ionized water. Finally, the wafer was washed with acetone and dried at 100℃ for 30 minutes. The film thickness was approximately 100nm after heat treatment. Al electrode was then vacuum-deposited onto the film. Fig. 1 shows the three-layered Schottky diode structure. The silicon layer was used as an electrode.
PPT Slide
Lager Image
Three-layered Schottky diode structure: TiO2 nanoparticle-TiO2 sol-gel acts as a semiconducting layer.
3. Results and Discussion
Fig. 2 shows surface FESEM images of (a) TiO-1, (b) TiO-5, (c) TiO-10, and (d) TiO-15. Nanoparticles were not observed on the surface of the TiO-1 film. Small individual particles were observed for the TiO-5. As the concentration of TiO 2 nanoparticles increased more than 10%, aggregated particles were observed on the surface of the films as shown in Fig. 2 (d) . Fig. 2(e) shows the cross sectional FESEM image of TiO-10. The thickness of the TiO 2 layer is about 75 nm.
PPT Slide
Lager Image
FESEM surface images: (a) TiO-1; (b) TiO-5; (c) TiO-10; (d) TiO-15 and (e) FESEM cross-sectional image of TiO-10.
Anatase and rutile crystallite phases are the main structures of TiO 2 , which have band-gap energies of 3.2 and 3.0 eV, respectively [11 , 12] . Anatase TiO 2 has excellent photocatalytic activity, long-term stability and nontoxicity [13] . Sol-gel spin-coating process is a promising technique over the other conventional techniques. The prepared films are mostly amorphous phase structures [14] . Fig. 3(a) shows the XRD patterns for the TiO-1, TiO-5, TiO-10 and TiO-15. There is no clear anatase or rutile diffraction peak for the TiO-1 and TiO-5. However, very weak major anatase (101) and rutile (110) diffraction peaks were observed for the TiO-10 and TiO-15. Fig. 3(b) shows XRD pattern for the TiO 2 nanoparticles. Strong anatase (101) and rutile (110) peaks are located at 25.4° and 27.5° respectively. The relative intensities of the anatase and rutile diffraction peaks are 54.7 and 45.3 %, respectively. It is clear that the TiO 2 nanoparticles are composed of anatase and rutile crystal structures.
PPT Slide
Lager Image
XRD patterns: (a) TiO-1; TiO-5, TiO-10, and TiO- 15. (b) TiO2 nanoparticles.
Schottky diodes fabricated with mixture of TiO 2 sol-gel and TiO 2 nanoparticles with different concentrations were characterized by measuring their I-V characteristics. The work function of Al is low (approximately 4.1 eV) compared with TiO 2 (5.1 eV for anatase structure and 4.9 eV for rutile structure) [11] . Therefore, the Al and TiO 2 nanoparticles and TiO 2 sol contact might be a Schottky junction due to a big difference in the work functions. Furthermore, due to the similar work function of Si (4.52 eV) and TiO 2 , the Si and TiO 2 nanoparticles and TiO 2 sol junction could be an Ohmic contact. Fig. 4 shows the result. The forward bias current was approximately 30 μA for the Schottky diode fabricated with pure TiO 2 sol-gel without TiO 2 nanoparticles. The forward current for the TiO-1 is approximately 130 μA, which is 4 times higher than the pure sol-gel Schottky diode. As the amount of TiO 2 nanoparticles increased, the forward current drastically increased up to 10 wt. % and decreased thereafter. The maximum forward current of 2.7 mA was achieved at 10 wt. % of TiO 2 nanoparticles. The improved forward current is due to the high quality crystallite nanoparticles of TiO 2 , which drastically increase the surface area of the active material. The reduction of the forward current for the TiO-15 might be due to the aggregation of the TiO 2 nanoparticles as shown in Fig. 2 (d) .
PPT Slide
Lager Image
I-V characteristics of Schottky diodes.
To distinguish the major conduction mechanism, various plots were employed based on the theoretical equation of each conduction mechanism. Three conduction models were employed by plotting Ln( J ) versus Ln( V ), Ln( J ) versus E 1/2 and Ln( J/V ) versus E 1/2 for the space charge limited conduction (SCLC), Schottky conduction (SC) and Poole-Frenkel conduction (PFC) models, respectively. Fig. 5 (a) , (b) and (c) represent the plots based on the SCLC, SC and PFC models, respectively. Table 1 shows beta values of SC and PFC mechanisms in linear regime. For both cases, beta values are too big compared with the theoretical values (3.03×10 -5 eV/ (V/m) 1/2 for SC and 6.06×10 -5 eV/(V/m) 1/2 for PFC) to match these mechanisms at low electric field [15] . The plot of SCLC model shown in Fig. 5(c) shows best linear fit in the experimental range. Therefore, SCLC process could be a major conduction mechanism [16] .
PPT Slide
Lager Image
The plots of three conduction mechanisms: (a) Ln (J) vs Ln(V) for SCLC. (b) Ln(J) vs E1/2 for SC and (c) Ln(J/V) vs E1/2 for PFC.
Beta values of TiO2nanoparticle doped TiO2solgel Schottky diodes of Schottky emission and Poole-Frenkel emission. Unit: ×10-5eV/ (V/m)1/2
PPT Slide
Lager Image
Beta values of TiO2 nanoparticle doped TiO2 solgel Schottky diodes of Schottky emission and Poole-Frenkel emission. Unit: ×10-5 eV/ (V/m)1/2
4. Conclusion
The mixtures of TiO 2 sol-gel and TiO 2 nanoparticles with different concentrations of TiO 2 nanoparticles were used as a semiconducting material for a Schottky diode fabrication. Although TiO 2 nanoparticles show strong anatase and rutile XRD peaks, the mixtures of TiO 2 sol-gel and TiO 2 nanoparticles exhibit no characteristic anatase and rutile diffraction peak. The forward current drastically increased as the concentration of TiO 2 nanoparticles increased until 10 wt. %. The forward current decreased as the TiO 2 concentration further increased. SCLC mechanism might be dominant for the linear regime.
Acknowledgements
This work was performed under the support of National Research Foundation of Korea (NRF-2013M3C1A3059586).
BIO
Mohammad Maniruzzaman He received B.S degree in Industrial & Production Engineering in 2009 from Bangladesh University of Engineering and Technology, MS in Mechanical Engineering from Inha University 2011. And now he is PhD student in Institute for Frontier Materials in Deakin University. His research interests are cellulose, nanocomposite, biosensors, liquid plasma, plant biology and plasma medicine.
Lindong Zhai He received his B.E. in Automotive and Mechanical Engineering in 2011 from Howon University and M.S. in Mechanical Engineering in 2013 from Inha University. Now he is PhD student in Mechanical Engineering in Inha University. His research is focus on cellulose nanocrystal and nanofiber.
Seongcheol Mun He received his B.S. and M.S. degrees of Mechanical Engineering from Inha University in 2010 and 1012, respectively. He is now Ph.D. student in Mechanical Engineering, Inha University. His research interests are renewable smart materials and its device applications.
Jaehwan Kim Prof. Kim received his Ph.D. degree of Engineering Science and Mechanics from The Pennsylvania State University, USA, in 1995. Since then he joined Mechanical Engineering department of Inha University where he is now Inha Fellow Professor. Prof. Kim is a fellow of The National Academy of Engineering of Korea and The Korean Academy of Science and Technology. His research interests are smart materials such as piezoelectric materials, electro-active polymers, electro-active paper, and smart devices such as sensors, actuators, motors and MEMS.
References
Chen T.L. , Furubayashi Y. , Hirose Y. , Hitosugi T. , Shimada T. , Hasegawa T. 2007 “Anatase phase stability and doping concentration dependent refractivity in codoped transparent conducting TiO2 films,” J. Phys. D: Appl. Phys. 40 (19) 5961 - 5964    DOI : 10.1088/0022-3727/40/19/026
Sakhno O.V. , Goldenberg L.M. , Stumpe J. , Smimova T.N. 2007 “Surface modified ZrO2 and TiO2 nanoparticles embedded in organic photopolymers for highly effective and UV-stable volume holograms,” Nanotechnol. 18 (10) 105704 -    DOI : 10.1088/0957-4484/18/10/105704
McFarland E.W. , Tang J. 2003 “A photovoltaic device structure based on internal electron emission,” Nature 421 616 - 618    DOI : 10.1038/nature01316
Miyazaki H. , Hyodo T. , Shimizu Y. , Egashira M. 2005 “Hydrogen-sensing properties of anodically oxidized TiO2 film sensors: Effects of preparation and pretreatment conditions,” Sensor Actuat. B-Chem. 108 467 - 472    DOI : 10.1016/j.snb.2004.10.056
Yu P. , Zhu K. , Norman A.G. , Ferrere S. , Frank A.J. , Nozik A.J. 2006 “Nanocrystalline TiO2 Solar Cells Sensitized with InAs Quantum Dots,” J. Phys. Chem. B. 110 (5) 25451 - 25454    DOI : 10.1021/jp064817b
Wang G. , Chen H. , Zhang H. , Shen Y. , Yuan C. , Lu Z. , Wang G. , Yang W. 1998 “Current-voltage characteristics of TiO2 /PPy complex films,” Phys. Lett. A. 237 (3) 165 - 168    DOI : 10.1016/S0375-9601(97)00837-2
Chen C. , Zhang W. , Zhao B. , Zhang Y. 2009 “Investigation of Schottky-Barrier carbon nanotube fieldeffect transistor by an efficient semi-classical numerical modeling,” Phys. Lett. A. 374 (2) 309 - 312    DOI : 10.1016/j.physleta.2009.10.083
Yang S.Y. , Kim J. , Song K.D. 2012 “Flexible patch rectennas for wireless actuation of cellulose electroactive paper actuator,” JEET 7 (6) 954 - 958
Nayak J. , Mahadeva S.K. , Chen Y. , Kang K.S. , Kim J. 2010 “Effect of ionic liquid dispersion on performance of a conducting polymer based Schottky diode,” Thin Solid Film 518 (19) 5626 - 5628    DOI : 10.1016/j.tsf.2010.05.049
Kang K.S. , Han K.J. , Kim J. 2009 “Polymer-Based Flexible Schottky Diode Made With Pentacene–PEDOT: PSS,” Nanotechnol., IEEE Trans. 8 (5) 627 - 630    DOI : 10.1109/TNANO.2009.2019640
Sclafani A. , Palmisano L. , Schiavello M. 1990 “Influence of the preparation methods of titanium dioxide on the photocatalytic degradation of phenol in aqueous dispersion,” J. Phys. Chem. 94 (2) 829 - 832    DOI : 10.1021/j100365a058
Rao M.V. , Rajeshwar K. , Verneker V.R., Pai , Dubow J. 1980 “Photosynthetic production of hydrogen and hydrogen peroxide on semiconducting oxide grains in aqueous solutions,” J. Phys. Chem. 84 (15) 1987 - 1991    DOI : 10.1021/j100452a023
Zhao Z. , Liu Q. 2008 “Mechanism of higher photocatalytic activity of anatase TiO2 doped with nitrogen under visible-light irradiation from density functional theory calculation,” J. Phys. D: Appl. Phys. 41 (2) 025105 -    DOI : 10.1088/0022-3727/41/2/025105
Rath H. , Dash P. , Som T. , Satyam P.V. , Singh U.P. , Kulriya P.K. , Kanjilal D. , Avasthi D.K. , Mishra N.C. 2009 “Structural evolution of TiO2 nanocrystalline thin films by thermal annealing and swift heavy ion irradiation,” J. Appl. Phys. 105 (7) 074311 -    DOI : 10.1063/1.3103333
Yoo K.H. , Kang K.S. , Chen Y. , Han K.J. , Kim J. 2009 “Direct and indirect contact effect between Al and TiO2 on the conduction mechanism for polymer-TiO2 Schottky diodes,” J. Phys. D: Appl. Phys. 42 (7)
Yoo K.H. , Kang K.S. , Chen Y. , Han K.J. , Kim J. 2008 “The effect of TiO2 nanoparticle concentration on conduction mechanism for TiO2-polymer diode,” Appl. Phys. Lett. 93 (19) 192113 -    DOI : 10.1063/1.3005591