JOURNAL OF OPTOELECTRONICS AND ADVANCED MATERIALS, Vol. 10, No. 9, September 2008, p.

2223 - 2227

Thermal decomposition study by DTA-TG-MS of cerium[III] acetylacetonate used as ceria thin film precursor
T. RISTOIU*, L. CIONTEA, R.-C. SUCIU, T. PETRISOR Jr., M.S. GABOR, Gy. THALMAYER, T. PETRISOR Materials Science Laboratory, Technical University of ClujNapoca, Str. C. Daicoviciu 15, Cluj-Napoca, Romania

Metal acetylacetonates (beta-di-ketonates), M(C5H7O2)z, are coordination compounds containing bidentate ligands. Due to their intrinsic properties they are extensively used as precursors both for solution and vapor deposition of oxide thin films. The cerium oxide (ceria) films have received a great interest due to their special optical and electrical properties. The potential applications of CeO2 films regard silicon-on-insulator structures, barrier layers, capacitor devices, solid oxide fuel cells, etc. The thermal decomposition of cerium(III) acetylacetonate hydrate in dynamical argon atmosphere and in static air has been studied by simultaneous differential thermal analysis-thermogravimetry-mass spectrometry (DTA-TG-MS) under a heating rate of 10oC/min. The DTA-TG-MS is powerful tool to analyze the complicated successive and superposed reactions accompanying the formation of the intermediate decomposition products to give the final cerium oxide. The total weight loss of 63.05 % is distributed in four major stages (calculated x=1.5). As it was revealed by the peaks observed in o o o the mass spectra (m/z = 43, 58, 27, 42, 15), the weight losses in the temperature range (60-194 C, 194-277 C, 277-350 C) o o can be attributed to the evolvement of acetone. The last stage, in the temperature range from 350 C to 720 C, is attributed to the acetic ion and carbon dioxide evolvement, as it was suggested by the MS peaks at m/z values (45, 43, 15) and m/z=44, respectively. (Received February 25, 2008; accepted August 14, 2008) Keywords: Acetylacetonate, Thermal decomposition, DTA-TG-MS, Ceria thin film

1. Introduction Cerium oxide thin films have a large range of applications in electronics, optics, catalysis, wear resistance, corrosion protection and superconductivity [1]. The cerium oxide, with a cubic fluorite structure (a=5.411), has been widely investigated as a buffer layer for YBa2Cu3O7-x (YBCO) superconducting coated conductors manufacturing. This interest is explained by the smaller lattice mismatch and the similar thermal expansion coefficient of CeO2 both with YBCO and the Ni based flexible metallic substrate [2]. Lately, many deposition techniques have been used for the deposition of CeO2 films, including both physical [3] and chemical methods [4]. Among the latter, the solgel processing route is particularly attractive for the scaling-up of oxide thin films fabrication, since the liquid precursor can easily be applied on a substrate by dipping, spinning or spraying [5,6] and heat treated at lower temperatures. -diketonate complexes, due to their high volatility, low decomposition temperature, ease of use, commercial availability and relatively low cost have become adequate precursors for metal oxides thin films. The quality of the thin films strongly depends on the thermal treatment and the reactions that take place during the decomposition of the precursor. Thermal analyses (TG-DTA) are powerful and highly reproducible methods, by which the weight and the nature

of the thermal processes of a sample can be monitored as a function of time and temperature with great accuracy. Nevertheless, the identification of the evolved gases cannot be performed. By coupling these methods with mass spectrometry analyses, in a simultaneous arrangement, it is possible to overcome this drawback. Thus, DTA-TG-MS becomes a very powerful technique that amplifies the capacity of both methods: for TG-DTA through the analysis of the evolved gases and for MS the possibility to measure temperature dependent mass spectra [7-9]. In this work we report on the thermal decomposition of cerium acetylacetonate (2,4-pentadionate) by a simultaneous DTA-TG-MS analysis, used as a precursor for the deposition of epitaxial CeO2 thin films on biaxially metallic substrates (Ni and Ni-based alloys) used as buffer layer for YBCO coated conductors. 2. Experimental Material The Ce(C5H7O2)3.xH2O used in this work with a purity of 99% has been purchased from Alfa Aesar. It is denoted in the text by Ce(acac)3. From the thermal analyses (see below), the solid-phase decomposition products were obtained by heating at 20-900C in air and

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T. Ristoiu, L. Ciontea, R.-C. Suciu, T. Petrisor Jr., M.S. Gabor, Gy. Thalmayer, T. Petrisor
30 25 20 10 0 -10 -20 dT in Ar 10 5 0 -5 -10 100 200 300 400 500
O

in a dynamic atmosphere of Ar (20 ml/min). The argon atmosphere was used to avoid charring the organic moieties. Apparatus
dT ( C )

dT in air

CeO (111)

Thermal analysis (TG-DTA) was performed in air and argon atmosphere, in the temperature range 20-900oC using an upgraded computer controlled equipment. The specimens (approximately 0.5 g) were weight in an Al2O3 crucible. The samples were heated at a rate of 10C/min from ambient temperature to 900oC in static air and in a dynamic atmosphere of Ar (20 ml/min). The TG-DTA has been hyphenated with a quadrupole mass spectrometer QMS 200 atmospheric sampling system, residual gas analyzer (RGA-Stanford Research System), through a 120 cm long stainless steel capillary of an internal diameter of 0.075 mm. The capillary was heated at about 100oC to prevent the condensation of water and other gaseous products. The acceleration voltage of the ionization was fixed at a potential of 70 eV. The mass region of m/z was fixed at 1-100 amu. We have used two operating modes for the RGA: successive scanning over its entire mass range and the registration of the evolution in time of ten chosen peaks. The structural characterization of the powder resulted at TG-DTA analysis was performed by Xray diffraction analysis (-2) using a Rigaku Geigerflex equipment with Cu K radiation. The diffractometer is equipped with a graphite monochromator on the diffracted beam to suppress the K component and parasitic scattering.

15

dm (%)

-30 -40 -50 -60 -70 900

dm in Ar dm in air

600

700

800

T ( C)

Fig. 1. TG-DTA plots of Ce(C5H7O2)3.xH2O in air and argon at a heating rate of 10oC/min.

It is to be noted that the compound is stable up to 60oC and that all the processes take place with weight loss. The melting temperature of Ce(C5H7O2)3.xH2O is 131132oC (Alfa AesarCatalogue 2002-03) evidenced by an endothermic peak, but accompanied by a slight weight loss indicates the superposition with other decomposition processes.

Intensitate ( u. a. )

CeO (220)

Fig. 1 presents the TG DTA curves in static air and in dynamic argon atmosphere for Ce(C5H7O2)3.xH2O. Actually, the so called argon atmosphere is poor in oxygen, but not inert, so that the oxidative processes are not completely hindered and the evolved gases can be identified more easily. Moreover, it is to be mentioned that the measurement does not take place in a closed system. The presence of a greater amount of oxygen significantly influences both the weight loss and the temperature at which certain thermal events take place, as well as their intensity. In spite of the fact that the weight loss takes place more rapidly in air with respect to argon, the total weight loss has the same value of 63%, attained in air at 600oC, while in argon at 720oC. The X-ray diffraction pattern of the resulted powder, Figure 2, evidences the presence of only CeO2. This enables the calculation of the molecular weight of Ce(C5H7O2)3.xH2O, from which results that x=1.5. Even at 500oC the X-ray diffraction patterns exhibits the presence of polycrystalline CeO2.

CeO (200)

CeO (311)

3. Results and discussion

CeO (331)

CeO (222)

CeO (400)

CeO (420)

20

30

40

50

60
O

70

80

2 (

Fig. 2. X-ray diffraction pattern of CeO2 powder resulted from the He TG-DTA (900oC) in air of Ce (acac)3xH2O.

In Fig. 3 and 4 the mass spectra present the evolution of the MS peaks with temperature in argon and in air, respectively superposed with TG analysis. The correlation between TG-MS is remarkable, demonstrating a short response time (1s) of the RGA and the accuracy of the method. Nevertheless, the presence of a larger amount of gases prolongues the MS signal after the end of the emission, leading to a broad band of overlapped effects.

CeO (422)

90

Thermal decomposition study by DTA-TG-MS of cerium[III] acetylacetonate used as ceria thin film precursor
100 10
-5

2225

200

300

400

500

600

700

800

900 10 0 -10

dm 10
-6

18

p (Torr)

10

-7

-20 17 44 -30 -40 -50 58 -60

Four major stages in the thermal evolution of Ce(acac)3.xH2O, both in argon and in air can be noticed. It is acetone that constantly appears in the first three stages, attributed to the thermal step-wise decomposition of each acetylacetonate ligand. The liberation of the acetate ion during the last stage indicates the presence of a mixed acetate-acetylacetonate-type product as a result of the cerium acetylacetonate decomposition.

dm (%)

10

-8

15 43

10

-9

45

1E-5

T = 146,8 C
1E-6

10

-10

100

200

300

400

T( C)
p (Torr )

500

600

700

800

-70 900
1E-7

Fig. 3. TG MS analysis of Ce(acac)3 xH2O, in Ar

1E-8

1E-9

100 10
-5

200

300

400

500

600

700

800

900 10
1E-10

dm 10
-6

0
18

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

m /z
-10
1E-5

17

p ( Torr)

10

-7

43 42

44

-20 -30 -40

dm (%)

T = 265,2 C
1E-6

15

10

-8

12 43

1E-7

10

-9

58

-50 -60

p ( Torr )

1E-8

10

-10

100

200

300

400

T ( C)

500

600

700

800

-70 900

1E-9

Fig. 4. TGMS analysis of Ce(acac)3 xH2O, in air.

1E -10 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

m /z

As far as the mass spectra are concerned, it can be seen that in argon atmosphere the liberation stages of the gaseous products are more evident. The 1-100 amu mass spectra continuously registrated during the heating and partially presented in Figure 5 at several significant temperatures have indicated that the main peaks correspond to acetone (m/z=58), carbon dioxide (m/z=44) and acetate ion (m/z=45). The confirmation of first sight identification has been performed by tracing the evolution of the representative ion fragment peaks corresponding to these compounds in agreement to the spectral data base (SDBS), as seen in Fig. 3 and 4. CO (m/z=28) evolvement could not be registered due to the overlapping with the nitrogen molecule. Nevertheless, it is presumed to convert to CO2 during the combustion process. The detailed analysis of these three types of measurements, DTA- TGMS, has led to correlation tables (Table 1-4) which reveal the main stages in the thermal evolution and the identified products.

1 E- 5

T = 3 43 ,2 C
1 E- 6

1 E- 7

p (Torr )

1 E- 8

1 E- 9

1 E -1 0 5 1 0 1 5 20 2 5 3 0 35 4 0 4 5 50 5 5 60 65 70 7 5 80 8 5 9 0 95 10 0

m /z

Fig 5. Mass spectra at different temperatures in Ar

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T. Ristoiu, L. Ciontea, R.-C. Suciu, T. Petrisor Jr., M.S. Gabor, Gy. Thalmayer, T. Petrisor Table 4. DTA-TG -MS correlation in air. Analyses Stage (oC) 60 - 192 192 - 250 250 - 300 300 - 600 TG DTA MS Evolved products m/m Peaks (oC) (%) 21,32 151 acetone (m/z=43,58,42,15) endo carbon dioxide (m/z=44,12) acetate ion (m/z=45,43,15) 29,2 220 acetone (m/z=43,58,42,15) endo carbon dioxide (m/z=44,12) acetate ion (m/z=45,43,15) 40,1 279 acetone (m/z=43,58,42,15) endo carbon dioxide (m/z=44,12) acetate ion (m/z= 45,43,15) 63,05 365 carbon dioxide (m/z=44,12) exo water (m/z =18,17), acetate ion (m/z=45,43,15)

Table 1. MS ion-MS peak temperature correlation in argon atmosphere.

m/z 15 17 18 43 44 45 58

MS ions CH3 OH H2O CH3CO CO2 COOH C3H6O

Temperature for MS peaks (oC) 156, 235, 320, 350-500 156 156 156, 235, 320, 350-500 156, 320, 350 320, 350-500 156, 235, 320

The lack of the peak with the m/z=60, as it can be seen in Figure 5, ascertains the absence of acetic acid as decomposition product, under our experimental conditions. But the acetate ion is present by the correlated evolution of the m/z=45, 43, 15 attributed peaks. At the same time, the prominent large exothermal peak is also associated with complex competitional oxidation processes, due both to the burning of the organic moieties and to the oxidation of Ce3+ to Ce4+.

All these considerations, as well as the thermal decomposition of other Me(acac)z [9,10], suggest intermediate compounds of Ce(C5H7O2)2(CH3COO), Ce(C5H7O2)(CH3COO)2, Ce(OH)(CH3COO)3, CeO(CH3COO) and CeOCO3 type prior to CeO2 crystallization. Further studies are necessary to elucidate the last decomposition stage. 4. Conclusions Under our investigation conditions, we have registered a continuous evolvement of acetone even at low temperatures, attributed to the successive decomposition of the three ligands. The DTA-TG-MS analysis represents a powerful method for the study of thermal processes which gives information about the evolved gaseous reaction products, but it does not offer enough information (under dynamic conditions) about the remaining products. Further investigation is necessary to establish the nature of the intermediate decomposition products. By this coupling we have succeeded to optimize a complex characterization method for oxide precursors for a better control of the precursor chemistry. Acknowledgements This work was supported by the European Community in the frame of EURATOM Project. References [1] M. S. Bhuiyan, M. Paranthaman, K. Salama, Supercond. Sci. Tecnol. 19, R1 R21 (2006). [2] A. Goyal, R. Feenstra, M. Paranthman, J. R. Thompson, B. Y. Kang, C. Cantoni, D. F. Lee, F. A. List, P. M. Martin, E. Lara-Curzio, C. Stevens, D. M. Kroeger, M. Kowalewski, E. D. Specht, T. Aytug, S. Sathyamurty, R. K Williams, R. E. Ericson, Physica C, 251-262 (2002).

Table 2. DTA-TG-MS correlation in argon atmosphere.

Analysis Stage (oC) 60 -194 194 - 277 277 - 350 350 - 720

TG m/m (%) 19,32 31,30 44,27 63,05

DTA MS Peaks Evolved products (oC) 148 water (m/z =18,17), endo acetone (m/z=43,58,15) carbon dioxide (m/z=44) 220 acetone (m/z=43,58,15) endo 318 acetone (m/z=43,58,15) endo carbon dioxide (m/z=44) 385 carbon dioxide (m/z=44) exo acetate ion(m/z=45,43,15)

Table 3. MS ion-MS peak temperature correlation in air.

m/z 12 15 17 18 42 43 44 45 58

MS ions C CH3 OH H2O CH2CO CH3CO CO2 COOH C3H6O

Temperature for MS peaks (oC) 158, 224, 320-366-600 158, 224, 297 477 366-600 366-600 158, 224, 297 158, 224, 297 158, 224, 320-366-600 158, 224, 320-366-600 158, 224, 297

Thermal decomposition study by DTA-TG-MS of cerium[III] acetylacetonate used as ceria thin film precursor

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[3] V. Boffa, T. Petrisor, S. Ceresara, L. Ciontea, F. Fabbri, P. Scardi, Physica C 312, 202 (1999). [4] Y. Akin, E. Celik, W. Sigmund, Y. S. Hascicek, IEEE Trans. Appl. Supercond. 13, 2563 (2003). [5] K. Knoth, B. Schlobach, R. Hunne, L. Schultz. B. Holzapfel, Physica C, 426431, 979 (2005) [6] L. Ciontea, T. Ristoiu, R.C. Suciu, T. Petrior Jr., T. Petrior, AIP Conference Proceeding, BPU 6, V.899, p.620 (2007).

[7] G. A. M. Hussein, H. M. Ismail, Powder Tech. 84, 185-190 (1995). [8] T. Arii, A .Kishi, M. Ogawa, Y. Sawada, Anal. Sci., V.17, 875-880 (2001). [9] A. G. Nasibulin, E. I. Kauppinen, D. P. Brown, J. K. Jokiniemi, J. Phis. Chem. 105, 11067 (2001). [10] A.Hakuli, A.Kytokivi, Phys.Chem.Chem.Phys., 1, 1607(1999).

_______________________ * Corresponding author: tristoiu@phys.utcluj.ro