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SYNTHESIS of Gd2O3 ALKOXIDE TYPE PRECURSORS for THIN FILM DEPOSITION by CHEMICAL METHODS R. C. Suciu*, I. Vida Simiti*, M.

M. Kulcsar** * Technical University of Cluj Napoca ** Babe Bolyai University

The chemical methods used for the deposition of oxide thin films represent a valid alternative to the physical deposition methods due to their versatility, relative simplicity, high deposition rate which makes them scalable. Among them, the gel processing route for oxide ceramics involve either the gelation of a sol by the removal of water, or the cross-linking of polymers by the partial hydrolysis of alkoxides in an alcoholic solvent. For both routes the final conversion to oxides is accomplished by heat-treating the dried gel, resulting in either polycrystalline or oriented (epitaxial) thin films. This last method has been investigated for the deposition of Gd2O3 buffer layers. The Gd-methoxyethoxide solution in 2-mehtoxyethanol has been prepared by refluxing the Gdisopropoxide with 2-methoxyethanol under argon, using moisture sensitive Schlenk type equipment. The coating solution was obtained by the partial hydrolysis of the Gd precursor solution. The characterization of the dried coating solution was performed by DTA-TG, X ray diffraction, FT-IR, NMR. This study represents the first stage in the fabrication process of Gd2O3 thin films deposited on various substrates, such as (001) SrTiO3, Ni and Ni based alloys (Ni- V, Ni-W) biaxially textured tapes, which are used as buffer layers for the YBa2Cu3O7- coated conductors. Keywords: oxide thin films, chemical methods, Gd2O3 buffer layer, epitaxy, alkoxides 1. Introduction High quality oxide thin films, epitaxial or polycrystalline, depending on the application, can be obtained both by physical and chemical methods. The physical methods, being vacuum techniques, require sophisticated and costfull deposition equipment. On the other hand, the chemical methods for the deposition of oxide thin films are accessible, versatile, easy to control and low cost. Furthermore, they ensure an atomic level homogeneity to the precursor, especially when a complex compound has to be obtained, high deposition rates with the possibility of scaling up. To epitaxially grow YBa2Cu3O7- (YBCO) superconducting thin films on biaxially textured metallic substrates such as Ni, or Ni based alloys (Ni-V, Ni-W), an intermediate epitaxial buffer layer is required. The role of the buffer layer is to decrease the difference between the lattice parameters of the substrate and the superconducting thin film, as well as between the thermal expansion coefficients. When Ni or Ni-based alloys are used as substrates, the role of the buffer

layer is to hinder the diffusion of Ni into the YBCO film, with negative consequences on the transport properties of the YBCO film. This paper presents our results regarding the epitaxial deposition of Gd2O3 thin films by chemical methods. The study on Gd2O3 thin films is motivated by the fact that they act as buffer layers for YBCO deposition on biaxially textured metallic tapes (Ni and Ni based alloys). The coating solution for the deposition of Gd2O3 thin films is obtained by the solgel process. The sol-gel process represents an adequate chemical route for the deposition of thinfilms. The gel processing route involve either the gelation of a sol by removal of water or the cross-linking of polymers by the partial hydrolysis of alkoxides in an alcoholic solvent. The special interest for the metal alkoxides is due to their homogeneous behavior at molecular level and their high chemical reactivity [3]. These two proprieties represent the most important aspects responsible for the use of metal alkoxides precursors for ceramic oxide materials [4]. To obtain the Gd2O3 buffer layer, the as obtained solution is spinned on various substrates: single crystalline (STO) SrTiO3 (100), Ni and Ni based alloys (Ni V, Ni - W) and afterwards heat-treated. 2. Experimental A. Preparation of the coating solution All solution manipulations were carried out under argon atmosphere using standard Schlenk techniques [1]. A gadolinium methoxyethoxide (Gd(OMeEt)3) solution in 2-methoxyethanol (MeEtOH) was prepared by charging a flask with gadolinium isopropoxide (Gd(iOPr)3) and 2methoxyethanol. The flask was refluxed for 1h and the solvent mixture (2-propanol and 2methoxyethanol) was removed by distillation. The content was rediluted with additional 2methoxyethanol, and the distillation/redilution cycle was repeated twice more to completely exchange the isopropoxide ligand for the methoxyethoxide ligand, according to reaction (1): Gd(iOPr)3 + 3MeEtOH Gd(OMeEt)3 + 3 iPrOH Where: Gd(iOPr)3 = Gd[OCH(CH3)2] 3 Gd(OMeEt)3 = Gd[CH3OCH2CH2O] 3 (1) ) MeEtOH = HOCH2CH2OCH3 iPrOH = (CH3)2CHOH

The reaction is quite rapid and follows no significant trend. The final concentration was adjusted with 2-methoxyethanol to produce a 0,25 M stock solution. The partial hydrolysis was performed with a 1M H2O in 2-methoxyethanol solution at a ratio of Gd(OMeEt)3: H2O = 4 : 1, according to reaction (2): Gd(OMeEt)3 + HOH Gd(OMeEt)x(OH)y + MeEtOH (2)

The flow sheet of the synthesis is presented in Fig. 1. Because it is not possible to purify

,,Fig. 1. Flow sheet of the coating solution preparation,, the gadolinium methoxyethoxide a viscous, brown nonvolatile oil - by either recrytallization or distillation, it was essential to start with very pure gadolinium isopropoxide, as purchased from Alfa Aesar. B. Coating of the precursor film Prior to the deposition, the substrate, both single crystalline STO and biaxially textured pure Ni and Ni-based alloys, were ultrasonically cleaned with isopropanol. The spin coating technique was used to coat single-crystalline STO (100) substrates. Prior to the deposition the 10 x 10 mm STO substrates were flooded with the coating solution and the excess solution was thrown-off by spinning under different conditions (from 10 to 25 seconds and 2000-6000 rpm), as presented in Fig. 2.

,,Fig.2 .The spin coating technique for the deposition of the precursor film[4] ,, C. Firing of the precursor film The as obtained films were heat-treated between 450 1000 C in air for one hour and quenced.

D. Analysis X ray diffraction analysis were performed with a Rigaku Geigerflex equipment. The DTA-Tg analysis were performed using a upgraded Edely Paulik DTA-TG computer controlled equipment. The IR spectra werw recorded with a FTIR Nicolet 205 a Specord IR 20 spectrophotometers in the 400-4000 cm-1 range in KBr pellets. The NMR spectra were recorded on a Varian Gemini 300s instrument operating at 299.5, 75.4 and 121,4 MHz. 3. Results and Discussion The Xray diffraction pattern of the hydrolysed Gd dried (110 C) precursor shown in Fig. 3, evidences its amorphous nature with a slight crystallization tendency.

,,Fig.3. The Xray diffraction pattern of the Gd dried (110C) precursor,, The broad peak observed at about 30 degrees can be attributed to gadolinium oxide carbonate (Gd2O2CO3) according to the Joint Committee of Powder Diffraction Files (JCPDF) 25 - 0339. The formation of Gd2O2CO3 can be explained by the air contamination of the partially hydrolysed moisture sensitive precursor. The DTA-TG analysis on the Gd(OR)x(OH)y precursor presents the mass variation with temperature and the endo- and exo- effects (Fig.4). The total weight loss associated with the transformation of Gd(OR)x(OH)y in Gd2O3 between 0-1200 C is 45,5 %. This weight loss is due to the volatilization of solvent and the dehydration process between 0 200 C, to the decomposition of the organic rest between 200 500C and the formation of a Gd(OH)3. As resulting from the TG curve, at temperature higher than 600 C the gadolinium hydroxide is completely transformed in Gd2O3. The observed DTA behavior above 600 C can be correlated with the crystallization of Gd2O3. The exothermic effect at 640 C can be attributed to the beginning of Gd2O3 crystallization.

,,Fig. 4. The DTA-TG analysis on the Gd(OR)x(OH)y precursor ,, The GdO crystallization kinetics has been investigated by X-ray diffraction. Thus, the precursor solution was deposited on the STO single crystal substrate and heat treated at different temperatures in the range from 450 C to 1000C. The results are presented in Fig. 5. As it can be seen, the (222) and (400) Gd2O3 peaks gradually increase with the temperature up to 900 C. Therefore, one can conclude that the crystallization process is over at this temperature. It is worthwhile to note that the peak intensities are not in accordance with those corresponding to polycrystalline samples. This can be explained by the epitaxial crystallization of Gd2O3 on (100) STO single crystalline substrate. The X-ray diffraction pattern for the sample heated at 1000 C shows the reflection peaks corresponding to Gd-Ti-O and Gd-Sr-O compounds which are formed at the Gd2O3 STO interface due to the high temperature treatment. The difficulty in interpreting these data is explained by the complex successive and superposed reactions that take place during the thermal treatment. The plausible first step, formation of an adduct and elimination of alcohol giving a hydroxyalkoxide, and thus an active functional OH group, is probably followed by a chain of polycondensation reactions of this hydroxyalkoxide with its self or with the starting Gd(OMeEt)3, this latter reaction being kinetically favored [2]. The proposed mechanism is:

(3)

(4)

(5)

,,Fig. 5. The X ray diffraction of the precursor solution deposited on the STO single crystal substrate and heat treated at different temperatures in the range from 450 C to 1000C(log scale) ,,

These polymerization reactions first offer metaloxane chains,

(6)

or two or threedimensional network polymers:

(7)

and finally the corresponding oxides. The absorption frequencies in the NaCl region of Gd(OR)x(OH)y of the FT-IR spectrum are: 3421,1 sh; 3069,16 sh; 2925,48 sh; 2360,44 sh; 428,03 sh; 1259,29 sh; 1259,29 sh; 120,44 m; 1065,48 m; 791,636 m; 729,925 m; 699,069 m; 486,081 s; 460,039 ; 446,442 s; 406,907 s (s strong; m medium; sh shoulder). This method will prove its use in the control of the synthesis only after a long series of analysis, both on reactants and on the reaction products, since no comparing spectra are available yet. Although NMR Spectroscopy has been used for the structure analysis of metal alkoxides, Gd such as most of the lanthanides ions, is paramagnetic [5] and this alkoxides cannot be analyzed by this method. 4. Conclusions We have demonstrated that a solution technique can be used to obtain epitaxy on various substrates, such as (001) SrTiO3. Considerable improvement to this process will be necessary to fully develop a conductor coated using only solution techniques, since the simplicity and the lowcost of this nonvacuum process are major incentives. References 1. D. C. Bradley, R. C. Mehrotra, D. P. Gaur In Metal Alkoxides. Academic Press, New York, 1978 2. K. S. Mazdiyasni, C. T. Lynch, and J. S. Smith, The Preparation and Same Properties of Yttrium, Dysprosium, and Ytterbium Alkoxides, Inorganic Chemistry, vol. 9. No. 12, 1970 3. J. S. Morell and co., Epitaxial growth of gadolinium oxide on roll-textured nickel using a solution growth technique, J. Mater. Res., Vol. 15, No.3, Mar 2000

4. Liliane Hubert-Pfalzgraf - Alkoxides as Molecular Precursors for Oxide Based Inorganic Materials: Opportunities for New Materials. New Journal of Chemistry, vol. 11, No 10 - 1987, p. 664-675 5. www.polymerprocessing.com/ operations/spcoat/