S. D. Gothe.et.al Int. Journal of Engineering Research and Application ISSN : 2248-9622, Vol. 6, Issue 9,(Part-5) September.2016, pp.26-32 RESEARCH ARTICLE www.ijera.com OPEN ACCESS Influence of Ruthenium doping on Structural and Morphological Properties of MoO3 Thin Films 1 S. D. Gothe, 2A.A.Wali, 3D. S. Sutrave, 1 Sangameshwar College, Solapur Maharashtra 413003 Devchand College, Arjun Nagar, Kolhapur, Maharashtra591237 3 D.B.F Dayanand College of Arts and Science, Solapur, Maharashtra 413003 2 ABSTRACT The present work examines the effect of Ru doping on MoO 3 thin films on steel substrate deposited by Sol-gel spin coat method. The annealing temperature was 600 0C for pure MoO3 and 8000C for Ru doped thin films. The doping concentration of Ru was varied from 10 to 50wt%. The influence of Ru doping on structural and morphological properties of MoO3 thin films were studied. The XRD revealed that all films are highly crystalline in nature with monoclinic phase for molybdenum peaks. In the doped XRD pattern some new peaks were observed and are matched with ruthenium orthorhombic phase indicating an incorporation of dopant in pure molybdenum oxide. The same is confirmed with the compositional analysis by EDAX. The SEM images of the MoO3 resemble a rod like surface with porous morphology. Incorporation of Ru ions in molybdenum oxide decreases the length of the rods and vanishes after 40wt%. Tetragonal grain size increases from 20wt% of Ru and becomes maximum at 50wt% of Ru doped thin films Key Words: XRD, SEM, EDAX, Sol-gel Spin Coating I. INTRODUCTION For the last several years, molybdenum oxide has attracted attentions because of their potential applications in gas sensing devices, optically switchable coatingsand catalysis etc[1-6]. It also exhibits electrochromism, photochromism after intercalating with an appropriate cation (such as Li+, Na+) making suitable for use in display devices,smart windows and electrochemical storage. Such a wide range applications is due to the non-stoichiometric nature of molybdenum oxide. The dependence of electrical property on oxygen concentration is such that MoO3is optically transparent [7-11] and electrically insulating in nature. In order to deposit MoO3thin film, number of methods have been adopted, such as electrodeposition12, thermal evaporation13 pulsed laser deposition, hot wire chemical vapour deposition,magnetron sputtering method, Sol-gel and Spray Pyrolysis etc[14-19]. In the present work, we reported our investigations on structural and morphological properties of molybdenum oxide MoO3and Ru doped MoO3thin films deposited by Sol-gel spin coat method. II. 1.2 Deposition Before deposition, the steel substrates were polished with zero grade polish paper and washed with double distilled water in an ultrasonic bath for 15 minute. To deposit the film by spin coat method, few drops of gel are placed on the steel substrate, which is then rotated at high speed (3000rpm) in order to spread the fluid by centrifugal force. The film thickness can be adjusted by varying the rotation speed, the rotation time, and the viscosity of the gel. After deposition, films were annealed under furnace. The annealing temperature for pure molybdenum film was 600 0C and Ru doped molybdenum films was 8000C. EXPERIMENTAL 2.1 Synthesis MoO3solution was prepared by dissolving Ammonium Molybdate Tetrahydrate with appropriate proportionin double distilled water. Once the solution became transparent, then drops of isopropyl alcohol were added as a solvent and www.ijera.com the mixed solution was stirred on magnetic stirrer at 500C for 4 hours and aged for 24 hours to yield a clear and viscous solution which was ready for sol gel spin coat deposition. The doped solution was prepared by adding to the precedent solution Ruthenium Trichloride as a dopant source. The weight percentages of Ru were 10%, 20%, 30%, 40% and 50%.The solution became clear and homogeneous after stirring for 4 hours at 500 to 700C on magnetic stirrer and aged for 24 hours to obtain viscous solution. III. RESULTS AND DISCUSSION 3.1 Structural Analysis by XRD The structural analysis was performed by using Bruker D8 Advanced instrument with source CuKα1 with λ =1.5406A0. The 2θ angle is varied from 200 to 900. Figure 1(a), (b), (c), (d), (e) and (f) 26|P a g e S. D. Gothe.et.al Int. Journal of Engineering Research and Application ISSN : 2248-9622, Vol. 6, Issue 9,(Part-5) September.2016, pp.26-32 shows the XRD patterns of the undoped and Ru doped MoO3thin filmswhich were deposited on the www.ijera.com steel substrates. All samples exhibited crystalline nature. 13000 20000 (a) 1 18000 (d) 4 2 12000 3 7 11000 16000 Intensity 14000 Intensity 10000 12 12000 4 5 6 7 11 8 11 9000 10 8000 14 10000 8 13 15 7000 9 8000 14 17 16 6000 20 18 18 6000 19 5000 4000 20 30 40 50 60 70 20 80 30 40 Angle 2 theta 50 60 70 80 Angle 2 theta 13000 7000 (b) 1 7 2 11000 6000 (e) 11 12000 8 34 10000 Intensity Intensity 5000 4000 4 3000 5 8000 10 13 7000 7 14 15 17 18 16 6000 8 2000 9000 9 19 20 11 5000 1000 20 20 30 40 50 60 70 30 40 50 60 70 80 90 Angle 2 theta 80 Angle 2 theta 14000 (f) 12000 3 11000 1 13000 (c) 4 2 12000 10000 11 7 11000 8000 Intensity 9000 Intensity 2 8 7000 6000 10 7 4 10000 8 9000 8000 10 7000 13 5000 3 14 15 4000 11 6000 16 17 18 13 17 18 16 5000 3000 15 14 19 20 4000 20 30 40 50 Angle 2 theta 60 70 80 20 30 40 50 60 70 80 Angle 2 theta Fig. 1 XRD patterns of Ru doped MoO3 films (a) 0 % (b), 10%, (c) 20%, (d) 30%, (e) 40%, (f) 50% The XRD patterns showed peaks for the planes [002], [311], [020], [111], [220] and [011] were matched with MoO3 phase of molybdenum oxide with monoclinic structure. The peaks for plane [002] and [311] were observed in only pure molybdenum sample. Remaining peaks for the plane [111] and [020] were observed in all the samples whereas, the dominating peak with plane [011] was disappeared after 20wt% Ru doping. Some peaks with plane [011], [211], [220], [031] and [202] were also observed in the XRD patterns of doped thin films which were matched with RuO2 phase with orthorhombicstructure. www.ijera.com 27|P a g e S. D. Gothe.et.al Int. Journal of Engineering Research and Application ISSN : 2248-9622, Vol. 6, Issue 9,(Part-5) September.2016, pp.26-32 www.ijera.com Table. 1 Detailed analysis of XRD patterns of pure and Ru doped MoO 3thin films It shows good agreement with the standard values (a=7.122Å, b=5.366Å, c=5.566Å) in JCPDS-891554 and (a=4.486Å, b=4.434Å, c=3.093Å) for MoO3and RuO2respectively. The effect of doping concentration on the values of lattice constants is shown in the graphical form in fig. 2 and 3. All peaks were matched with JCPDS card No. 89-1554, and 88-0323 for MoO3and RuO2 respectively. The detailed analysis of all XRD peaks and intensity variation for all the peaks is given in table.1. Lattice constants ‘a, ‘b’ and ‘c’ for MoO3and RuO2are calculated from the XRD data. 7.3 7.2 a 7.1 Lattice constans 7.0 5.6 5.5 b 5.4 5.3 5.8 c 5.7 5.6 5.5 5.4 0.0 0.1 0.2 0.3 0.4 0.5 Ru Doping concentration (at wt%) Fig. 2 Variation in lattice constants of MoO3with doping concentration www.ijera.com 28|P a g e S. D. Gothe.et.al Int. Journal of Engineering Research and Application ISSN : 2248-9622, Vol. 6, Issue 9,(Part-5) September.2016, pp.26-32 www.ijera.com a1 4.6 4.4 4.2 Lattice constants 4.0 4.8 b1 4.6 4.4 4.2 3.4 c1 3.2 3.0 2.8 0.1 0.2 0.3 0.4 0.5 Ru doping concentration (atwt%) Fig. 3Variation in lattice constants of RuO2 with doping concentration 3.2 Surface Morphology by SEM Morphological studies have been carried out using a scanning electron microscope JEOL JSM-6360 instrument. The variation of grain size with doping concentration is calculated from the SEM images and is given in fig.4. Figure 5(a), (b), (c), (d), (e) and (f) shows the SEM images of the undoped and Ru doped MoO3films. SEM image of pure MoO3resembles a granular surface with tetragonal and rod like structure. Incorporation of Ru modifies the surface morphology. With enhancement in doping concentration porosity of film surface increased and also grains with rod like structure become smaller in size and completely vanished after 30wt% Ru. In 10wt% doped film small clusters were formed and size of these clusters increased upto 30wt% Ru and at 50wt%, surface morphology completely changed to petals like granular structure with maximum grain size. Fig. 4 Variations in grain size with doping concentration www.ijera.com 29|P a g e S. D. Gothe.et.al Int. Journal of Engineering Research and Application ISSN : 2248-9622, Vol. 6, Issue 9,(Part-5) September.2016, pp.26-32 www.ijera.com Fig.5 SEM images of Ru doped MoO3 films(a)0%(b) 10%, (c) 20%, (d) 30%, (e) 40% and (f) 50% 3.3 Compositional Analysis by EDAX EDAX analysis is carried out using Quanta 200 ESEM instrument. The EDAX spectrum of pure and Ru doped MoO3thin film is shown in Figure 6(a), (b), (c), (d), (e) and (f). Table. 2 gives the ratio of Mo:Ru:O elemental www.ijera.com composition. EDAX analysis showed that the amount of doped element in the sample increased depending on the increasing doping concentration in the solution. As a result Ru incorporation has a strong effect on structural and morphological properties of MoO3thin films. 30|P a g e S. D. Gothe.et.al Int. Journal of Engineering Research and Application ISSN : 2248-9622, Vol. 6, Issue 9,(Part-5) September.2016, pp.26-32 www.ijera.com Fig.6 EDAX patterns of Ru doped MoO3 films (a) 0%, (b)10%,(c)20%,(d) 30%,(e) 40% and (f) 50% Doping Concentration (%) 0.00 10.00 20.00 30.00 40.00 50.00 IV. Experimental Result (Weight %) Mo Ru O 53.38 0 46.61 44.34 1.05 54.60 41.13 1.21 57.54 32.48 2.05 65.45 31.82 2.42 65.74 31.08 2.69 66.22 Table. 2 Composition analysis by EDAX CONCLUSION Ru doped MoO3thin films were prepared with different values of Ru content by the sol-gel spin coating method. The diffraction patterns reveal a good crystalline behaviour for all the films with the monoclinic and orthorhombic phase for MoO3 and RuO2 diffraction peaks. SEM micrographs showed that incorporation of dopant changes the surface morphology of films by changing grain structure and grain size. Maximum porosity was observed for 30wt% of Ru. The EDAX analysis of thesamples were done with the Mo/Ruweight ratio www.ijera.com and it is confirmed that, Ru is well incorporated in MoO3.As a result Ru incorporation has a strong effect on structural and morphological properties of MoO3thin films. REFERENCES [1]. [2]. J. Okumu, F. Koerfer, C. Salinga, M. Wutting, J. Appl. Phys. 95,7632(2005) S. H. Mohamed, O. Kappertz, J.M. Nagaruiya, T. P.L. Pedersen, R. Drese,and M. Wutting, Thin solid Films 429,135 (2003) 31|P a g e S. D. Gothe.et.al Int. Journal of Engineering Research and Application ISSN : 2248-9622, Vol. 6, Issue 9,(Part-5) September.2016, pp.26-32 [3]. [4]. [5]. [6]. [7]. [8]. [9]. [10]. [11]. [12]. [13]. [14]. [15]. [16]. [17]. [18]. [19]. www.ijera.com J. Okumu, F. Koerfer, C. Salinga, T. P. Pedersen, M. Wutting, Thin SolidFilms 515, 1327(2006) Hsu. C. S, Chan. C. C, Huang. H. T, Peng. C. H and Hsu. W. C,J. Thin Solid Films 516, 4839 (2008) Okumu. J, Koerfer. F, Salinga. C, Pedersen. T. P and Wuttig. M,J. 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