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J Sol-Gel Sci Technol (2009) 52:124133 DOI 10.



Solgel chemistry of an aqueous precursor solution for YBCO thin lms

Tran Thi Thuy S. Hoste G. G. Herman K. De Buysser P. Lommens J. Feys D. Vandeput I. Van Driessche

Received: 26 March 2009 / Accepted: 28 April 2009 / Published online: 19 May 2009 Springer Science+Business Media, LLC 2009

Abstract A water based YBa2Cu3O7-x (YBCO) precursor using a triethanolamine (TEA)/acetic acid complexing method to obtain YBCO thin lms is described in detail. The inuence of complexation behavior in the formation of transparent and homogenous sols and gels after the combination of Y, Ba and Cuacetates, acetic acid and TEA has been studied by potentiometric titration and the results are compared with analytical simulations. The decomposition of the gel was studied by IR (infrared) and Thermal Gravimetric Analysis/Differential Thermal Analysis (TGA/ DTA). The results in sol-gel chemistry can be used to decide on the necessities in the preparation of stable sol gel precursors with a minimum amount of organic compounds. The solgel system was also used for the deposition of high textured superconducting thin lms on STO substrates by dip coating. The synthesized YBCO showed a superconducting transition temperature of 90.95 K with narrow DT (2 K) for thin lms. The results from X-ray diffraction show that the single phase YBCO was obtained. SEM pictures also indicate that the properties of the surface thin lms are good. Keywords Potentiometric titration Solgel Thin lms YBCO Superconductors

1 Introduction Soon after the discovery of superconducting materials [1], the quest for the practical applications led to the investigation on the current carrying capacity of this new material at the boiling point of liquid nitrogen. Compared with other cuprates, YBCO [2] seems to be the most promising material because of the current carrying ability in a magnetic eld and a high current density self-eld [3]. Clearly the understandings of the unique properties of these copper-based superconducting oxides, as well as their technological applications, depend crucially upon composition, homogeneity and microstructure [4]. These three parameters are of utmost importance during synthesis. From this point of view, several review articles on the synthesis of high temperature superconducting oxides have appeared [46]. Compared with the other methods, the solgel process [7] has the potential advantage not only of achieving homogeneous mixing of the component cations on atomic scale, but also forming lms or bers which are of great technological importance [4]. A variety of strategies such as colloidal sol gel, inorganic polymeric gel derived from organometallic compounds and gel routes involving formation of organic polymeric glasses with success in obtaining a homogeneous YBCO precursor solution without precipitation has been documented [35]. However, a suitable technological precursor solution should contain minimal amounts of organic compounds, expected to leave less carbon residue which is detrimental for the superconducting properties [8]. For this reason, this paper is devoted to the preparation of a water based precursor system and to the control of the composition of the solution to obtain a clear gel with minimal amounts of organic compounds. Potentiometric titrations and IR measurements were used to study the composition of the solutions and the decomposition of the gels.

T. T. Thuy (&) S. Hoste G. G. Herman K. De Buysser P. Lommens J. Feys D. Vandeput I. Van Driessche Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent, Belgium e-mail:


J Sol-Gel Sci Technol (2009) 52:124133


We have selected and studied the combination of two candidate materials (TEA and acetic acid) in order to establish the preparation of a stable precursor solution which can be used for dip coating of superconducting layers. Furthermore, simulation programs were employed to build up models expressing the inuence of complexation behavior in the formation of transparent and homogenous sols and gels. From this stable precursor solution, YBCO thin lms on STO were synthesized. Texture analysis of the YBCO layers was performed using XRD scanning and SEM imaging. The voltage measurements were applied to determine the critical transition temperature of superconductor thin lms.

25 C 0.1 C by a circulating water bath thermostat. All systems were studied under protected conditions, established by a stream of saturated nitrogen obtained by bubbling inert gas though a 0.1 M KNO3 solution [9]. The data were processed using Grans method [10] in order to determine the cell potential E, the Nernstian slope s, the dissociation constant of water (Kw) together with the correction terms for changes in the liquid junction potential for non-linear electrode response in strong acid medium, aj (pH \ 2.3) and in strong alkaline medium, bj (pH [ 11.0). This method is also needed in order to calculate the carbonate content of the strong base which can interfere in the calculation of the protonation and stability constants.

2 Experimental 2.1 Chemicals Yttrium, barium, and copper nitrates, and acetates, KNO3, HNO3, TEA and EDTA were purchased from SigmaAldrich (Germany). Ammonia (25 wt%) and glacial acetic acid (99 wt%) were obtained from Chem-Lab (Belgium). The standard KOH solution was obtained from VWR (France). Thermo Gravimetric Analysis/Differential Thermal Analysis (TGA/DTA) was performed on the starting Y, Ba and Cu acetates to determine the water content of the metal acetates in order to assure a 1: 2: 3 stoichiometry of Y3?, Ba2? and Cu2? in the precursor solutions. The metal ion stock solutions using for potentiometric titrations were prepared using metal nitrates. Acidbase titrations were used to standardize the metal ion stock solutions by the method of back titration. A known excess of ethylenediaminetetraacetic acid (EDTA) was added to the analyte metal nitrate. The excess EDTA was titrated with a standard potassium hydroxide solution. All nal solutions for the potentiometric experiments have an ionic strength of 0.1 M (KNO3). To determine the concentration of the triethanolamine (TEA) solution, an excess of nitric acid was added which was then titrated with KOH. 2.2 Potentiometric measurements The potentiometric measurements were performed using a Schott pH meter and a 5 mL Schott T-burette. The pH meter was connected to a Schott H2680 glass electrode and a Schott B3410 calomel electrode with a second salt bridge lled with 0.1 M KNO3. Each aqueous system under consideration was titrated with a standard carbonate free KOH solution in a 100 mL jacketed cell thermostated at

2.3 Preparation of YBCO precursor solutions and interpretation of EQUIL data The scheme to make YBCO precursor solutions is indicated in Fig. 1. By adding a high concentration of TEA (1.7 mol TEA per mol metal ions) and a low amount of acetic acid (8% vol.), a clear precursor solution can be obtained (Fig. 2). The solutions could be stored at room temperature for several weeks without loosing stability. The models of the EQUIL program [11] were built on the stability constant data taken from the literature [1214]. The detailed models are shown in Tables 1 and 2.

Y, Ba, Cu acetates (aq)

Reflux 90C, 1h TEA (1.7 mol TEA per mol metal ions)

Glacial acetic acid (8 vol% aq)

Clear dark blue 0.6M solution pH = 6.5, = 3.126 cP

Clear dark blue gel

Fig. 1 The schematic of aqueous YBCO precursor solution synthesis



J Sol-Gel Sci Technol (2009) 52:124133 Table 2 The stability constant data of Cu2? with acetic acid and TEA taken from [1214] used as model for the EQUIL program logb Stoichiometry Cu2? HOAc TEA H

Model 1: copper TEA hydroxo complexes 4.03 4.56 1.83 3.09 7.80 Fig. 2 Picture of clear and homogeneous sol and gel -19.32 -13.78 -1.90 Table 1 The stability constant data of Y3?, Ba2? with acetic acid and TEA taken from [12, 13] used as model for the EQUIL program logb Stoichiometry Y 7.80 4.56 1.68 3.17 -22.00 -13.78 0 0 1 1 1 0 Ba2? 7.80 4.56 0.39 -2.30 -13.78 0 0 1 1 0

1 0 1 1 0 1 0 1 1 2 2 2

0 1 1 2 0 0 0 0 0 0 0 0

1 0 0 0 1 0 0 1 1 2 2 2

0 1 0 0 1 -2 -1 -1 -2 -2 -3 -4

Model 2: model 1 ? copper TEA mono and dihydroxo complexes -9.70 -1.10 HOAc 0 1 1 2 0 0 HOAc 0 1 1 0 0 TEA 1 0 0 0 0 0 TEA 1 0 0 0 0 H 1 1 0 0 -3 -1 H 1 1 0 -2 -1 -8.20 -16.20

Model 3: model 2 ? dimer copper TEA hydroxo complexes

3 Results and discussion 3.1 Characterization of precursor solutions To obtain an YBCO precursor solution, a suitable ligand should be used in order to complex with yttrium, barium and copper ions. Soluble complexes are formed, so the concentration of free metal ions will be reduced and a clear precursor solution can be obtained. The question is how to choose a suitable ligand for the solution which has three metal ions having different polarizing characters (cationic change/ionic radius). The very weak polarizing character of barium makes it very difcult to precipitate with hydroxides [15]. The solubility of barium hydroxide in water is 5.6/100 g. It is an advantage to make an YBCO precursor solution because the coordination of hard barium ions with all ligands is very weak. However, we have noticed that the behavior of copper and yttrium aqueous solutions are quite similar and decided to focus on these two elements in order to obtain homogeneous sols and gels. In this study, TEA and acetic acid were chosen as complexing agents. TEA is both a tertiary amine and a trialcohol. The potentially tetradentate TEA forms stable complexes with Cu2? [11, 12] using its nitrogen and neutral oxygen donors [16]. Acetic acid is used to complex with the harder metal ions Y3? and Ba2? as well as Cu2? [16]. Acetic acid was present with a ratio higher than 1 in comparison with metal ions. It leads to the equilibrium: M(CH3COO)n  Mn? ? nCH3COO- shifting to the left side at higher acetateconcentrations thereby lowering the

The compositions of species are given with stoichiometric coefcients. A negative coefcient for H means bonded OH-

2.4 Other techniques The infrared spectra were recorded with a Bruker Equinox 55 instrument in the spectral range between 4,000 and 400 cm-1, using the KBr pellet technique. The thermal decomposition behavior of the gel network was investigated separately by TGATGA measurements (STD 2960 Simultaneous DSC-TGA) on bulk samples with the same composition as dip coated layers. Identication of different phases present in the YBCO lms was performed by X-ray diffraction (Siemens D5000, CuKa). The overall morphology of the lms was characterized by SEM (Philip 501). The critical temperature of the superconductive layers was determined by voltage measurements (National instruments Labview 8.0).


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free concentration of Mn? according to Le Chateliers principle. Mono dentate metal acetates are retained in the precursor solutions together with [CuTEA]2?. An YBCO precursor solution with only acetic acid present as a complexant should be adjusted to pH = 6.0 in order to achieve homogeneous gels without phase separation [4]. However, this solution is only stable in a narrow pH region. During the gelation there is a shift in pH which results in precipitation. Therefore, the ideal precursor solutions should contain a second stronger ligand such as TEA. TEA will only form complexes with Cu2? and the acetic acid will avoid precipitation of Y3?. Titrations of solutions containing yttrium ions, acetic acid and TEA were performed in the stoichiometric ratio Y3?: acetic acid: TEA of 1:3:3. The experimental pH curves were tted to the calculated ones using the stability constant data from literature. Figure 3 shows the t for a ratio of Y3?: acetic acid: TEA of 0:3:3 and 1:3:3. As indicated in the experimental curve, the rst inection point at a = 0 matches the end of the neutralization of the excess HNO3 added to the ligand solution, where a is the ratio between mol of base added and mol of ligand. The second inection point at a = 1 corresponds to the completion of neutralization of acetic acid. The third one at a = 2 matches exactly with the full deprotonation of TEA. The quality of t was excellent from very acidic media to pH about 7 where acetic acid was totally deprotonated. At higher pH, Y(OH)3 starts to precipitate due to the high free concentration of yttrium. This can not avoid by TEA. It leads to a lowering of the pH in the solution and the titration could not be continued as shown in Fig. 3. This was also demonstrated by the simulation curve 7 where Y(OH)3 was included. The quality of t of simulation curve (7) and the experiment curve (4) was perfect as

can be seen in Fig. 3. It can be inferred from these titrations that yttrium ions only complex with acetic acid with the stability constants given in the Table 1. Titrations of solutions containing copper ions, acetic acid and TEA were also carried out in different stoichiometric ratios of Cu2?: acetic acid: TEA of 1: 3: m (m = 1, 2 or 3). The experimental pH curves were tted to the calculated ones using the stability constant data from the literature and a selection of candidate complexes as described in the Table 2. Figure 4 shows the t for a ratio of Cu2?: acetic acid: TEA of 1: 3: 1 with different models. When all kinds of copper TEA hydroxo complexes were excluded (model 1), the quality of t was not good from pH 6 onwards. The pH value of the simulation curve was higher than the one of the experimental curve that indicates some protonated reactions occurred. Therefore, copper TEA mono- and dihydroxo complexes were included and the quality of t improved signicantly (model 2). However, there was still a small difference between the experimental and calculated curve at pH [ 5 where acetic acid has been deprotonated. In the solution, there are some protonated reactions. Therefore, all kinds of copper TEA mono, dihydroxo complexes and dimer copper TEA mono, dihydroxo complexes were taken into account (model 3). The quality of t was excellent from very acidic media to pH about 9 where TEA is fully deprotonated. Nevertheless, there is a slight but systematic difference between the experimental and calculated curve from pH value of 9 on. In this pH range, only the copper dihydroxo TEA complexes [Cu(TEA)(OH)2] and its dimer [Cu2(TEA)2(OH)4] were the governing species. The pH value of the experimental curve is lower than the pH value of the simulated curve which means that it still incenses the protonation of

Fig. 3 The simulation and experimental curves for the reaction of KOH with HNO3, acetic acid and ?HTEA with and without Y3? plotted as pH versus a (where a = mole of base added/mole ligand)



(1) OAcTEAH-simulation (2) OAcTEAH-experiment (4) YOAcTEAH-experiment (5) YOAcTEAH-simulation (7) YOAcTEAH-simulation when Y(OH)3 added (3) OAcTEAH-a-dpH/da-experiment (6) YOAcTEAH-a-dpH/da

(1) and (2) (5)





(4) (6)




2 -1.5

0 -1 -0.5 0 0.5 1 1.5 2


128 Fig. 4 The simulation and experimental curves for the reaction of KOH with HNO3, acetic acid and ?HTEA with and without Cu2? plotted as pH versus a (where a = mole of base added/mole ligand)

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(1)-TEAOAc-simulation (2)-TEAOAc-experiment (3)-CuTEAOAc-simulation (model 3) (1) and (2) (4)


(4)-CuTEAOAc-experiment (5)-CuTEAOAc-simulation (model 2) (6)-CuTEAOAc-simulation (model 1) (7)-a-dpH/da -experiment (6)










2 -1.5

0 -1 -0.5 0 0.5 1 1.5 2 2.5 3 3.5

some species. Those species should contain hydrogen. It might be assumed that a tetramer [17] was existent. With the ratio of Y3?: Cu2?: acetic acid: TEA of 1: 3: 13.98: 10.2 as in the precursor solution, the distribution of different species was calculated using the stability constant data from literature. The result is shown in Fig. 5. One can see that coordination by acetate starts at about pH 2.5. At pH 3.5 also TEA starts to coordinate with Cu2? to form

[Cu(TEA)]2?. The maximum amount of this complex is reached at pH 5.7. From pH value of 6.5 on, the Cu-TEA hydroxo complexes becomes dominant. The free concentration of Cu2? becomes negligible when pH reaches 6.5. The complexes between Cu2? and acetic acid decrease dramatically from pH 5 and drop to zero from pH 6.5 on. Dimeric species have been found at neutral and basic pH. It is seen that in the solution dihydroxo complexes

100 90 80 70 60

pH area (5.7 to 6.5) to produce clear, stable and homogeneous sol and gel






50 40 30 20 10

[Cu(TEA)(OH)]+ [Cu(TEA)(OH)2] [Cu2(TEA)2(OH)2]2+ [Cu2(TEA)2(OH)3]+ [Cu2(TEA)2(OH)4] [Cu(OAc)]+ [Cu(OAc)2]






[Y(OAc)]2+ [Y(OAc)2]+ Y(OH)3


[Cu(TEA)(OH)]+ [Cu(TEA)(OH)2]

[Y(OAc)2]+ [Cu(OAc)2]

0 2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5 10.5

Fig. 5 Distribution of species which contain Y(III), Cu(II) ion, acetic acid, TEA, at 25 C, I = 0.1 M (with ratio of Y3?: Cu2?: acetic acid: TEA in 1: 3: 13.98: 10.2)


Table 3 Wavenumbers (cm-1) and assignments of the vibrational modes of the gel and heat treated samples of precursor solution between 4,000 and 500 cm-1 400 C Y2O3 CH stretch of CH3 CH stretch of CH2 CH stretch of CH3 OH and NH stretch from (OHCH2CH2)3NH? [1821] [1821] [19, 21] [19, 21] [24] [22] [20] MeO stretch Symmetric carboxylate ions CO2dCH3 dCH3 ? m(CCO2-) 1,066w 866 vw 694 m 859 w 670 w 1,061 w 855 s 693 s 669 s mCO with dip(COH) dCH3 mCNC q\ (CH3) BaO stretch qk (CH3) mCC MeO mCC MO stretch dCOOp (CH) or p (COO) [19, 20] [20] [23] [23] [22] [23] [23] [20, 22] [20, 22, 23] [22] See text [22] [20] BaO BaCO3 CuO Assignment Ref. 3,405 3,411 3,421 500 C 600 C

Gel (IR)

200 C

300 C

3,340 s, br

3,380 s


3,147 m

2,975 w

2,929 w

2,923 w

2,896 w

2,358 w, sh 2,358 w, sh 2,358 w, sh 2,358 w, sh 2,358 w, sh 2,358 w, sh 2,358 w, sh 2,358 w, sh 2,358 w, sh 2,358 w, sh CO2 from atmosphere and from heat treated sample 2,323 w, sh 2,323 w, sh 2,323 w, sh 2,323 w, sh 2,323 w, sh 2,323 w, sh 2,323 w, sh 2,323 w, sh 2,323 w, sh 2,323 w, sh 1,727 w 1,425 m 1,058 w 858 m 690 m 694 m 858 m 858 m 1,056 w 1,056 w 1,428 m 1,430 w 1,425 w 1,437 m 1,450 s dCH3 C=O of HOAc 1,747 w 1,747 w 1,752 w 1,652 w Ba=O stretch of BaO BaO stretch of BaCO3

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1,727 w

1,727 w

1,641 w

1,554 s

1,550 s

1,546 s

Antisymmetric carboxylate ions CO2- [19, 20]

1,484 w

1,452 vw

1,401 s

1,409 s

1,407 s

1,338 vw

1,340 vw


1,321 w

1,290 w

1,251 w

1,238 w


1,226 w

1,191 w 1,133 w

1116 w

1106 w

1,091 w

1,078 w

1,064 w

1,049 w

1,047 w

1,027 m

1,020 w

1,016 w

1,004 w

916 s

914 m

935 w

848 vw


750 vw

740 vw

761 vw

675 w, sh

671 w, sh

669 w, sh

650 w

651 w

651 w

615 w

617 w

613 w



130 Ref.

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[Cu2(TEA)2(OH)4] and [Cu(TEA)(OH)2] are only present at alkaline medium. As mentioned earlier, Y3? and Ba2? do not coordinate with TEA. A low free concentration of Y3? can only be reached at pH above 5.7. In order to minimize the concentration of three metal ions Y3?, Ba2? and Cu2?, the optimal pH value of the precursor solution should be higher than 5.7. To avoid the yttrium hydroxide the maximum pH should kept lower than 6.5. Under these pH conditions, the precursor solution produces clear, stable and homogeneous sols and gels. 3.2 Characterization of YBCO gels

YO stretch of Y2O3



YO stretch of Y2O3

3.2.1 FTIR The band positions measured for gel and its decomposition and some reference samples are indicated in Table 3. These assignments are mainly based on some general references [1821] as well as on some specic spectroscopic studies of complexes [22, 23]. Some aspects of these assignments are momentarily commented below. IR spectra during the heat treatment are shown in Fig. 6. The band at high frequency (3,340 cm-1) due to the OH stretch from water and NH stretch from (OHCH2CH2)3 NH? became smaller. Bands at 2,3652,345 cm-1 belong to carbon dioxide from the atmosphere and from the decomposition of the gel during heat treatment [24]. The acetate complexes started to decompose at 200 C indicated by a change in intensity and to lower wave numbers. At 400 C the acetate complexes were decomposed completely. There was a shift from 1,410 to 1,430 cm-1 during the heat treatment (200600 C) due to the decomposition of the gel and the formation of MO bonds. The bands at 1,058 and 858 cm-1 were observed for samples heat treated at higher temperatures, due to the formation of BaCO3. The band at 673 cm-1 due to the MO stretch gained more intensity during heat treatment as expected. The other bands due to organic compounds such as CH2, CN lowered in intensity and disappeared almost completely at 400 C. 3.2.2 DTATGA In order to obtain information about the decomposition behavior of the gels to adjust the thermal treatment accordingly, a TGADTA analysis was carried out in air atmosphere. The heating rate was 10 C/min. Three main areas can be distinguished in the thermogram shown in Fig. 7. The rst broad endothermic peak can be correlated to the evaporation and the release of acetic acid and gel network water just below 200 C. The exothermal peak at 233 C coupled to the large loss in mass can be attributed


466 w 466 w 466 w 482 w 480 w 465 m

Band intensity: s strong; m medium; w weak; sh shoulder; vs very strong; vw very weak; sh shoulder; br broad


565 s 564 w 565 w

600 C

500 C

400 C

300 C

Table 3 continued

200 C

Gel (IR)


538 w

522 w

543 sh


J Sol-Gel Sci Technol (2009) 52:124133 Fig. 6 FTIR spectra of the gel and heat treated samples




901 1732 2355 500C 1049 300C 200C 300C 400C 500C 600C 1340 1020 1228 858 468


615 654 673



3371 1552 1410

0 3900 3400 2900 2400 1900




Wavenumer, cm-1

Fig. 7 TGADTA spectrum of YBCO gel

free water and acetic acid

1 0.8 0.6
Weight Temperature difference

415 C

crystal water


0.4 0.2

233 C 476 C

155 C NOx

0 -0.2


116 C carbondioxide CuO2 Y2O2CO3 CuO BaCO3 BaO

-0.4 -0.6 -0.8



0 0 100 200 300 400 500 600 700 800 900

-1 1000

Temperature, C

to an auto combustion reaction due to the presence of acetate groups. The second exothermal peak at 415 C corresponds to the decomposition of the intermediary products CuO2, Y2O2CO3. The nal combustion of the network mainly involves the release of relatively large quantity of CO and CO2. After this reaction the remaining species consist of yttrium, barium and copper oxides. These metal oxides then convert to the desire YBCO phase at the sintering temperature of 800 C.

3.3 Characterization of YBCO thin lms Since the solgel process was conducted on STO single crystals one may expect high degree alignment of the YBCO coating. The SEM micrograph of YBCO layer deposited from the precursor solution reveals that the thin lm surface is continuous as well as crack free. The SEM image suggests that the resulting superconducting layer is polycrystalline with some degree of misorientation of


Temperature difference, C/mg


Weight, %


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in resistivity, in Fig. 10, between 280 and 90 K (which directly can be calculated from the voltage measurements) may suggest insufcient oxidation of the superconductor. Alternatively frequent ab plane c-axis inter-grain connections observed in Fig. 8 may be also responsible for this effect. The value of critical current density measurement is still very low about 0.2 MA/cm2. Therefore, a further study and optimization of superconducting properties of the thin lms will be the subject of the next paper.

4 Conclusions The inuence of complexation behavior in the formation of transparent and homogenous sols and gels by the combination of Y, Ba and Cuacetates, acetic acid and triethanolamine has been studied and interpreted using simulated metal-ligands equilibriums with the EQUIL program. From the t between experimental data from potentiometric titration with simulated distributions of a large set of different complex species, the occurrence of different species at different pH values could be inferred. FTIR was applied to study the decomposition of the gel. Based on these results, the preparation of waterbased precursors for the synthesis of superconducting YBCO could be optimized. The synthesized YBCO material showed a superconducting transition temperature of 90.95 K with narrow DT (2 K) for the thin lms. The further study and optimization of superconducting properties of the thin lms will be the subject of the next paper.

Fig. 8 SEM micrograph of the YBCO layer deposited from the precursor solution

surface grains. However, the XRD diffraction patterns in Fig. 9 indicate predominantly (001) peaks, but this may reect the ake-like nature of the superconducting grains. As can be seen in the Fig. 8, a few particles (indicated by arrows) that have been identied as a copper-rich phase originated from decomposition process of YBCO at high temperature [25]. The Tc measurement in liquid nitrogen given in Fig. 10 clearly shows a sharp superconducting transition of YBCO thin lm at 90.95 K with a narrow DT (2 K). The low drop

Fig. 9 XRD of YBCO thin lm coated on STO substrate



Lin (Cps)



STO 002

K 001 004 111 007

0 5 15 25 35 45 55



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T = 90.95 - 88.90 = 2.05K

10 2

0 280 230 180 130 80

Temperature /K

Fig. 10 Tc measurements for YBCO thin lm Acknowledgments The authors would like to thank Olivier Janssens (Ghent University, Belgium) for XRD and SEM measurements. 13. Smith RM, Martell AE (1977) Critical stability constants vol 3. Plenum Press, New York 14. Tauler R, Casassas E, Rainer MJA (1985) Inorg Chim Acta 105:165. doi:10.1016/S0020-1693(00)90556-5 15. Martell AE, Hancock RD (1996) Metal complexes in aqueous solutions. Springer, 253 pp 16. Barboux P, Valente I, Tarascon JM et al (1989) Mater Res Soc 156:189 17. Whitmire KH, Hutchison JC, Gardberg A et al (1999) Inorg Chim Acta 294:153. doi:10.1016/S0020-1693(99)00274-1 18. Steele D (1971) The interpretation of vibrational spectra. Chapman and Hall Ltd., London. doi:10.1016/0022-2860(73)85247-0 19. Dollish FR, Fateley WG, Bentley FF (1974) Charateristic Raman frequencies of organic compounds. Wiley, New York. doi: 10.1016/0022-2860(74)87027-4 20. Nakamoto K (1997) Infrared and Raman spectra of inorganic and coordination compounds, part B: applications in coordination, organometallic and bioinorganic chemistry, 5th edn. John Wiley & Sons 21. Socrates G (2001) Infrared and Raman characteristic group frequencies: tables and charts, 3rd edn. John Wiley & Sons ` 22. Quiles F, Burneau A (1998) Vib Spectrosc 16:105. doi:10.1016/ S0924-2031(98)00004-6 23. Baran EJ, Wagnera CC, Torreb MH (2002) J Braz Chem Soc 13:576. doi:10.1590/S0103-50532002000500006 24. Leleckaite A, Kareiva A (2004) Opt Mater 26:123. doi:10.1016/ j.optmat.2003.11.009 25. Lian J, Haibo Y, Donglu S et al (2003) Supercond Sci Technol 16:838. doi:10.1088/0953-2048/16/8/302

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dE/dT, microvolt/K

T-E dE/dT


E, microvolt