IPASJ International Journal of Electrical Engineering (IIJEE)

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Volume 1, Issue 6, December 2013

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Preparation of ITO thin film by Sol-Gel method

Harith Ibrahem1, Mariam Moghdad2
1,2

University of Baghdad

ABSTRACT
Highly transparent and conductive thin films ITO have been prepared on glass substrate using spray pyrolysis method. The ITO deposited at substrate temperature 400 C their thickness was approximately (150 nm), and at different doping ratios(5,10,15,20) of Sn Wt.% annealed at ( 500-550 )C for one hour . The structural, optical and electrical properties for all films were studied. X-ray diffraction data showed that all films have polycrystalline nature cubic for ITOwith major reflex along (222) plane .The absorbance and transmittance spectra data for the films were recorded at room temperature in the wavelength range (200-1100nm), which were used to determine the optical properties of the films. All films are highly transparent (greater than 91%) in visible region of electromagnetic spectrum, the direct band gap was in the range (3.6-3.88 ) eV.

Keywords: ITO, Sol-Gel, Thin film

1. INTRODUCTION
TIN-DOPED indium oxide films, commonly referred to as ITO films, are n-type, degenerate semiconductors with wide band-gap, which have high transmittance, high infrared reflectance, good electrical conductivity, excellent substrate adherence and chemical inertness hence [1],[2] they have been extensively used as coating electrodes for optoelectronics such as organic light-emitting diodes (OLEDs), liquid crystal displays (LCDs), solar cells, etc. in recent years, ITO films are used extensively and play the leading role in the field of display ,ITO films need additional fine patterning when they are used in the concrete integrated apparatus so as to obtain specified fine patterns It is difficult to obtain a fine pattern at a sub-nanometer scale through conventional chemical etching methods, such as wet etching, dry etching, etc. [3],[4].ITO particles have been obtained by various techniques, such as thermal hydrolysis, thermal decomposition, spray pyrolysis, and coprecipitation However, these methods have not proved very successful in obtaining nanometric particles due to the high degree of agglomeration presented by the oxide. Other methods that have been used include direct precipitation, co-precipitation, and hydrothermal methods, but these do not allow for control of the particle size distribution new techniques for obtaining metal oxides with controlled morphological characteristics have recently been developed Among these techniques, the sol-gel method stands out for its advantages, such as the possibility of obtaining high purity materials using simple equipment Another advantage of the sol-gel method is the ability to process the material in the form of thin films, which, in the particular case of ITO, is the only technique that allows for deposition on relatively large substrates at a feasible cost,the sol-gel methodology comprises wet and dry routes one of the dry routes is the sol-gel method for nonhydrolytic gels (NHG), developed in the 1990s as an alternative to the hydrolytic sol-gel route one of the advantages of the NHG method is the greater homogeneity achieved for heterometallic oxides, not easily achieved by the hydrolytic sol-gel route due to the different reactivities of their alkoxidesPromising results have been obtained through the NGH method, which not only allows for greater reproducibility but also involves the use of less expensive precursors, thus representing lower costs and better quality [5],[6]. Although the sol-gel process is one of the candidates for the fabrication method of ITO films, a subsequent heattreatment at a relatively high temperature is needed for crystallization and removal of residual organic and hydroxyl groups recently, various irradiation techniques using energetic ions and ultraviolet (UV) light were applied to modification of sol-gel films as an alternative to conventional heat-treatments. These studies revealed that collisional atomic displacements and electronic excitations could densify sol-gel derived films at low temperatures [7]. some previous works showed that the best performances, can only be obtained for an annealing temperature around 550 C. The lowering of this high sintering temperature still remains a challenge as regards the use of the solgel process for the coatings on plastic substrates or smart textile the aim of our study is to investigate the electrical properties, optical properties of the solgel derived ITO films as a function of metal concentration of the sol [8],[9].

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ITO is a wide-gap, degenerated semiconductor where electrons are the major charge carriers the Sn atoms are considered to substitute for In, without ordering the difference of valence between In3 and Sn4 results in the donation of a free electron to the lattice for most applications, the ITO films must be as conducting as possible, which requires a high carrier density (n c) and a high carrier mobility () [10].

2. Experimental Section
To prepare ITO thin film ,firstly we prepared Indium chloride solution(sol I) which prepared by dissolving (0.5g of InCl3 molecular weight 221.18 g/mole ) in (25ml) of methanol the solution was stirred for half hour on magnetic stirr .the second solution is the tin chloride solution (sol II) (SnCl2.2H2O molecular weight 225.6 g/mole) which is used as a dopant solution depending on the weight of the tin chloride in (15ml)of methanol where the doping ratio of the tin with Indium was token from the following equation [11] (5,10,15,20)% The last solution was also stirred for half hour on magnetic stirr , then it add gradually to the Indium chloride solution. The final solution stirred again at lest for 20 minuet a few drops of Hydrochloric acid were add as a catalyst, this solution called ITO solution.this solution leaves for one day to be gelation. In this work a microscopic glass and quartz slides of dimension, (25 25 1) mm are used as a substrate .this substrate must be thoroughly cleaned before deposition, In the present study the cleaning of the substrates was done by cleaning the substrates with deionized water, then they immersed in the ethanol and put in an agitated ultrasonic bath at least for half hour , finally the substrates were dried by lens paper and dry air.Spray pyrolysis, which is a process in which a thin film is deposited by spraying a solution on a preheated substrate , where the constituents react to form a chemical compound. the substrate temperature reach to (400-450 ) C in this temperature the solution was sprayed on the substrate then left to dry for about 20 minute , this process was returned twice to get the suitable thickness . The produced film from the above process must be annealed to get the completely oxidization process . so they put into the oven at temperature about (500-550) C for glass and at (600) C for quartz substrates ,for one hour and then left in the oven until it reach to the room temperature . Thefilm crystalline structure was investigated by a used X-ray instrument is supplied by SHIMADZU 6000 X-ray diffractometer (illustrated in figure 2- 7) using Cu K radiation (1.5406 ) in reflection geometry. A proportional counter with an operating voltage of 40 kV and a current of 30 mA is used. XRD patterns are recorded at a scanning rate of (0.08333) s-1 in the (2 ) ranges from (20 to 60). The SEM study carried out by (Hitachi FE-SEM model S-4160, Japan) in University of Tehran, The optical properties of the prepared thin films deposited on quartz slides which includes the transmittance spectra are studied over the wavelength range (200-1100nm) by using Shimadzu UV/Visible recorder spectrometer model (Centra 5).

3. RESULT AND DISCUSSION

The X-ray diffractions pattern of the ITO thin films for the four doping ratio (5,10,15,20) wt. % of Sn with In are shown in figure(1) The analyses evidence at low doping ratio the film has low crystallinaty comparing with other films as illustrated in figure (3-1-a); also we can observed from experimental data appearing of peaks at (222) ,(400) and (440) which refers to cubic structure of In2O3 the intensity of this peaks are very low ; this means that the interaction did not reach the level of saturation which are compensate tin atoms within the structure of In2O3 [12] . By increasing doping ratio above (5%) the films begin to take a polycrystalline nature [13, [14]. The growing of the peaks (400),(440) of cubic In2O3 crystal also can be observed but with lower intensity than (222) plane [15].No phases corresponding to tin or other tin compounds were detect showing that the Sn was in solution in the In2O3. As a result the crystallinaty increase because substitutional replacement of indium by tin in the lattice took place.

Figure (1) X-ray diffraction pattern of ITO films prepared at (5,10,15,20) wt. % of Sn.

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The SEM pictures of the ITO film which it prepared by chemical spray method on a glass substrate at temperature (400C)and annealed for one hour at(500-550) C for the doping ratio of (20) Wt.% of Sn with In are demonstrated in the regions (a,b,c,d,e,f) where all regions showing the identity of the film except region (e) that explain a patch resulting from sudden spray of the solution on the hot substrate . The mean average value of the grains was found to be about (60nm) for regions (a,b,d) , (1m) for (c) ,(0.2m) for(e) and (10 m) for(f),this convert from the nano to the micro scale associated with the increasing the crystallization of the film so that in the region (d) we can see the cubic shapes which for the In2O3 crystal [16]. All regions are approximately homogenous so this will more affects on the optical and electrical properties [17],[18].

Figure 2 UV-VIS transmittance spectra of the ITO/quartz films with thickness of (150) nm and different doping ratios of Sn Wt. %

Figure (3) shows the optical transmittance as a function of wave length in the range (2001100) nm) with different doping ratios of (5,10,15,20) Wt. % Sn of thickness (150) nm. This reveals that the transmittance depends on the Sn doping . The maximum transmittance observed at 5% equal to (96.7%) in the wavelength (600)nm , while for 10%,15% films the maximum transmittance equal (92%) and (83.2%) at 20% doping Sn . The behavior of the transmittance spectra is opposite completely to that of the absorption spectra. In general, we can observe from this figure that transmittance decreases with increasing of doping ratios of Sn and this may be due to impurities and decreases in the hemogensaty of the film which means an increase in the absorption. The films were found to be highly transmittance in the visible wavelength region with an average transmittance in excess of 91% [19],[20],[21]. The energy gap values depend in general on the films crystal structure, the arrangement and distribution of atoms in the crystal lattice; also affected by crystal regularity. The optical energy gap (Eg) was derived assuming a direct transition between the edge of the valence and conduction band. The optical energy gap values (Egopt) for ITO films have been determined by using Tauc formula by plotting the relations of (h)2 vs E (eV) for direct energy gap as shown in figure (3-6).The energy gap is obtained from intercept of the extrapolated linear part of the curve with the energy axis, the direct band gap of the ITO films increases from (3.7-3.88)eV when doping ratio increases from 5% Wt.Sn to 20%Wt.Sn . We can see that at 5% optical energy gap approximately equal to 3.7eV,for 10% equal to 3.6eV,for 15% equal to 3.7eV and for 20% doping Sn equal to 3.88eV. Mean that the lowest optical energy gap in the doping ratio of 10 % Sn in this ratio the mobility increases because of the increase in the carrier concentration and this led to narrowing optical band gab because of the modification of structure . So the shift in the optical energy gap to

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approximately 3.88eV for 20% Sn attributed to the decreases in the carrier concentration there for in this ratio the mobility will decreases because of increasing optical energy gap[22].Our results are nearly in agreement with [23],[24],[25].

4. Conclusions
The analyses evidence at low doping ratio the film has low crystallinaty comparing with other films .By increasing doping ratio above (5%) the films begin to take a polycrystalline nature. Appearing of peaks at (222) ,(400) and (440) which refers to cubic structure of In2O3 the intensity of this peaks are very low at low doping ratio and it increase with increase doping ratio.No phases corresponding to tin or other tin compounds were detect showing that the Sn was in solution in the In2O3.The SEM pictures for the doping ratio of (20) Wt.% of Sn with In, all regions are approximately homogenous so this will more affects on the optical and electrical properties. The transmittance decreases with increasing of doping ratios of Sn from(96.7%-83.2%) this may be due to impurities and decreases in the hemogensaty of the film which means an increase in the absorption The direct band gap of the ITO films increases from( 3.7-3.88) eV when doping ratio increases from 5% Wt.Sn to 20%Wt.Sn , the lowest optical energy gap in the doping ratio of 10 % Sn(3.6) eV, in this ratio the mobility increases because of the increase in the carrier concentration and this led to narrowing optical band gab because of the modification of structure of the ITO films.

References
[1] C. Su*,T.-K. Sheu ,Y.-T.Chang ,M. A. Wan, M.-C. Feng ,and W.-C.Hung ,"Preparation of ITO thin film by sol gel processand their charictarization" , Synthetic Materials 153,9-12,(2005). [2] Ying Li, Gaoyang Zhao, Weihua Zhang, and Yuanqing Chen," Using the Photolysis of Chemically Modified Gel Films Preparing ITO Fine Patterned Thin Films", Journal of Display Technology, vol. 2, No. 2, (2006). [3] Ju-O Park, Joon-Hyung Lee, Jeong-Joo Kim, Sang-Hee Cho, Young Ki Cho, "Crystallization of indium tin oxide thin films prepared by RF-magnetron sputtering without external heating" ,Thin Solid Films 474, 127 132,(2005). [4] Zheng Jiao*, Minghong Wu, Zheng Qin, Minghua Lu, Jianzhong Gu," The NO2 sensing ITO thin films prepared by ultrasonic spray pyrolysis " Sensors, 3, 285-289 , (2003). [5] T.F.Stoica , M.Gartner, , M.Losur do, V.T eodorescu, M.Blanchin, Spectroellipsometric study of the solgel nanocrystalline ITO multilayer films, Thin Solid Films 455 456 ,509512,(2004) [6] Ying Li, Gaoyang Zhao, Yang Ren and Dichun Chen, Microstructure analysis of sol-gel-derived nanocrystalline ITO thin films Surf. Interface Anal., 43, 11991202,(2011). [7] Hiroaki Imai, Atsushi Tominaga and Hiroshi Hirashima , Ultraviolet-Laser-Induced Crystallization of Sol-Gel Derived Indium Oxide Films, Journal of Sol-Gel Science and Technology 13, 991994 (1998). [8] A. Beaurain, D. Luxembourg, C. Dufour, V. Koncar, B. Capoen, M. Bouazaoui , Effects of annealing temperature and heat-treatment duration on electrical properties of solgel derived indium-tin-oxide thin films "Thin Solid Films 516 ,41024106, (2008). [9] T.F. Stoica, M. Gartner', T.A. Stoica and M. Zaharescu'ELLIPSOMETRIC STUDIES OF INDIUM TIN OXIDE FILM DEPOSITED BY SOL-GEL PROCESS National Institute of Materials Physics, POB Mg7,(1999). [10] Hai-Ning Cui, V. Teixeira, Li-Jian Meng, R. Martins, E. Fortunato , Influence of oxygen/argon pressure ratio on the morphology, optical and electrical properties of ITO thin films deposited at room temperature ,Vacuum 82 ,15071511, (2008). [12] Masayuki Okuya, Nobuyuki Ito, Katsuyuki Shiozaki ITO thin films prepared by a microwave heating Thin Solid Films 515 (2007) 86568659 2007. [13] K BISWAS*, A DE, L K DUA and L CHKODA Surface characterization of solgel derived indium tin oxide films on glass Bull. Mater. Sci., Vol. 29, No. 3, June 2006, pp. 323330.(2006)

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[14] M.J. AlamU, D.C. Cameron Optical and electrical properties of transparent conductive ITO thin films deposited by sol-gel process Thin Solid Films 00 _2000. 455-459 [15] Seon-Soon Kima, Se-Young Choia,*, Chan-Gyung Parkb, Hyeon-Woo Jinb Transparent conductive ITO thin lms through the sol-gel process using metal salts Thin Solid Films 347 (1999) 155-160 [16] Sutapa Roy Ramanan Dip coated ITO thin-films through sol_gel process using metal salts Thin Solid Films 389 (2001). 207_212 [17] Gabriel M. Silva, Emerson H. de Faria, Eduardo J. Nassar*, Katia J. Ciuffi e Paulo S. Calefi ,SYNTHESIS OF INDIUM TIN OXIDE NANOPARTICLES BY A NONHYDROLYTIC SOL-GEL METHOD Quim. Nova, Vol. 35, No. 3, 473-476, 2012. [18] H.H. Dabaghi1, Y. Ganjkhanlou2, M. Kazemzad2, A.B. Moghaddam3,4 Relation between conductance, photoluminescence bands and structure of ITO nanoparticles prepared by various chemical methods Micro & Nano Letters, Vol. 6, Iss. 6, pp. 429433 2011. [19] Lszl Krsi a, , Szilvia Papp a, Imre Dkny a,b, Preparation of transparent conductive indium tin oxide thin films from nanocrystalline indium tin hydroxide by dip-coating method Thin Solid Films 519, 31133118,(2011). [20] M. Purica a, F. Iacomi b, C. Baban b, P. Prepelita b, N. Apetroaei b, D. Mardare b, D. Luca b Investigation of structural properties of ITO thin films deposited on different substrates Thin Solid Films 515 (2007) 86748678 ,2007. [21] Miaoju Chuang ITO Films Prepared by Long-throw Magnetron Sputtering without Oxygen Partial Pressure J. Mater. Sci. Technol., , 26(7), 577-583,2010. [22] C. Guillen*, J. Herrero Comparison study of ITO thin films deposited by sputtering at room temperature onto polymer and glass substrates Thin Solid Films 480481 (2005) 129 132 (2005). [23] Chih-hao Yang a, Shih-chin Lee a, Tien-chai Lin b, Suz-cheng Chen a Electrical and optical properties of indium tin oxide films prepared on plastic substrates by radio frequency magnetron sputtering Thin Solid Films 516 (2008) 19841991 2008. [24] C. Guillen_, J. Herrero Influence of oxygen in the deposition and annealing atmosphere onthe characteristics of ITO thin films prepared by sputtering at room temperature Vacuum 80 (2006) 615620 (2006). [25] Hamid Reza Fallah a,*, Mohsen Ghasemi a, Ali Hassanzadeh b, Hadi Steki c The effect of annealing on structural, electrical and optical properties of nanostructured ITO films prepared by e-beam evaporation Materials Research Bulletin 42 (2007) 487496 2007.

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