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Applied Surface Science


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Structural and dielectric properties of Ba(X1/3 Ta2/3 )O3 thin lms grown by RF-PLD
L. Nedelcu a, , N.D. Scarisoreanu b , C. Chirila a , C. Busuioc a,c , M.G. Banciu a , S.I. Jinga c , M. Dinescu b
a b c

National Institute of Materials Physics, 077125 Bucharest-Magurele, Romania National Institute for Laser, Plasma and Radiation Physics, 077125 Bucharest-Magurele, Romania University Politehnica of Bucharest, 011061 Bucharest, Romania

a r t i c l e
Article history: Available online xxx

i n f o

a b s t r a c t
Ba(X1/3 Ta2/3 )O3 (X = Mg, Zn) thin lms were grown on commercial Pt-coated Si substrates by radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) method. Single phase Ba(Mg1/3 Ta2/3 )O3 and Ba(Zn1/3 Ta2/3 )O3 ceramic targets having an ordered hexagonal structure (with P3m1 space group) were used for deposition. Structural, morphological and surface characterizations of the Ba(X1/3 Ta2/3 )O3 (BXT) lms were performed using X-ray diffraction, scanning electron microscopy and atomic force microscopy. X-ray diffraction studies evidenced a cubic (disordered) perovskite structure, with unit cell typical for Pm3m space group. Scanning electron microscopy investigations showed that BXT lms have a columnar microstructure, which is oriented perpendicular to the substrate. The temperature dependence of the dielectric permittivity of the lms was recorded at 100 kHz. Unlike targets, the BXT lms exhibit positive values of the temperature coefcient of the dielectric permittivity. BaMg1/3 Ta2/3 O3 and BaZn1/3 Ta2/3 O3 thin lms with dielectric constant of about 22.5 and 25, respectively have been obtained. 2012 Elsevier B.V. All rights reserved.

Keywords: Complex perovskites Thin lms RF-PLD, X-ray diffraction Dielectric properties

1. Introduction Since the 1980s, many temperature-stable microwave dielectrics have been developed and employed in wireless communication systems [1]. Among the materials involved in applications, bulk ceramics are by far the most utilized as they offer cost-effective solutions for manufacturing companies [24]. The continuous miniaturization of devices has an important role in raising the requirements for dielectric materials and processing technologies. Therefore, new generations of devices based on dielectric thin lms are required in the integration of microelectronics systems. Barium tantalate-based ceramics have been extensively studied due to their low dielectric loss in microwave and millimeter wave domain [14]. At low synthesis temperature, such complex perovskites as Ba(X1/3 Ta2/3 )O3 (X = Mg, Zn) form a disordered cubic structure (X and Ta cations arranged randomly). For appropriate synthesis temperature or/and time, this cubic phase (with Pm3m space group) can be transformed into an ordered hexagonal structure, in which the 1:2 long-range ordering of X and Ta cations in the { XTaTaXTaTa } repeat sequence along the 1 1 1 direction of the parent cubic cell yields a superstructure with P3m1

symmetry [1,5]. Despite the fact that Ba(X1/3 Ta2/3 )O3 (BXT) bulk materials have been intensively investigated [1], only few papers reporting the dielectric properties of the Ba(Mg1/3 Ta2/3 )O3 and Ba(Zn1/3 Ta2/3 )O3 thin lms are available in the literature [610]. In a previous paper [11], we reported the structural and optical properties of Ba(Mg1/3 Ta2/3 )O3 (BMT) thin lms grown on (1 0 0) silicon and r-cut sapphire substrates using radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) method. We showed that single-phase BMT lms with attractive optical and dielectric characteristics at room temperature can be achieved by using the RF-PLD hybrid technique. The aim of this work is to investigate the temperature behavior of the complex dielectric constant of the BMT lms grown in the best experimental conditions. As Ba(Zn1/3 Ta2/3 )O3 (BZT) bulk ceramics exhibit attractive characteristics for wide frequency band electronics [14], BZT thin lms were also deposited and investigated in this paper. Since the temperature stability is an important issue for applications, the dielectric properties of the BXT thin lms were investigated in a wide temperature range.

2. Experimental The BMT and BZT thin lms were grown on commercial Ptcoated silicon wafers (Si/SiO2 /TiO2 /Pt) by the RF-PLD method. Hexagonal Ba(Mg1/3 Ta2/3 )O3 and Ba(Zn1/3 Ta2/3 )O3 ceramic targets prepared by using solid-state reaction at 1650 C have been used

Corresponding author. Tel.: +40 213690170; fax: +40 213690177. E-mail address: nedelcu@inm.ro (L. Nedelcu). 0169-4332/$ see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.apsusc.2012.10.124

Please cite this article in press as: L. Nedelcu, et al., Structural and dielectric properties of Ba(X1/3 Ta2/3 )O3 thin lms grown by RF-PLD, Appl. Surf. Sci. (2012), http://dx.doi.org/10.1016/j.apsusc.2012.10.124

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for deposition. A detailed description of targets preparation and characterization is presented in previous works [12,13]. Unlike the classic pulsed laser deposition technique, RF-PLD method gives an important advantage for thin lm deposition of oxides materials [14,15]. The advantage is due to the assistance of a radiofrequency plasma beam, generated in owing oxygen between two parallel electrodes. The enhanced reactivity of the gas species, oxygen in this case, has an important role in preserving the lm stoichiometry and in decreasing the problems related to oxygen vacancies. As experimental conditions, a Surelite II Nd:YAG laser (265 nm wavelength, 5 ns pulse length, 54,000 laser pulses and 10 Hz repetition rate) has been used, in conjunction with BMT and BZT targets which were simultaneously rotated and translated. The laser uence values were 3.5 J/cm2 for BMT thin lms and 2.4 J/cm2 for BZT thin lms, respectively. The Pt-coated Si substrates were heated to 700 C, the oxygen partial pressure being maintained at 0.5 mbar. The substrates used were placed at a distance of 4.5 cm from the target. The substrates were heated to the deposition temperature with a ramp of 50 C/min. After deposition, the lms were cooled to room temperature in oxygen background gas with a 10 C/min rate. The RF power was set at 100 W during depositions. The presented experimental conditions were chosen as a result of a parametric study performed on these materials. For these experimental conditions, the resulting thin lms exhibit the best structural, stoichiometric and dielectric properties. A detailed description including the system gures was presented in previous works [14,15]. Structural analyses were performed on BXT lms with a BrukerD8 Advance diffractometer, equipped with a copper target X-ray tube and a scintillation detector. An asymmetric channel cut Ge crystal installed after the Goebel mirror provided a strictly monochromatic CuK 1 primary X-ray parallel beam. The diffraction diagrams were recorded from 15 to 60 in the /2 mode, with 0.02 steps and 5-s counting time per point. A corundum plate reference material (NIST SRM 1976) was used for checking the 2 calibration of the instrument in order to make correct unit-cell parameter calculation and to subtract the effect of the instrumental line width from the line broadening. Morphological analyses were performed on BXT lms by using a HITACHI S2600N Electronic Microscope. The atomic force microscopy morphologic investigations were carried out with a Park XE 100 system in tapping mode. The electrical parameters were measured using an Agilent 4263B LCR meter. The capacitance-temperature characteristics of the BXT lms were recorded at 100 kHz in the 50 to +100 C temperature range. The samples were rst cooled down to 50 C, and then the temperature was increased to +100 C with a 1 C/min rate. The temperature control was performed by using a Janis CCS 400EB cryostat.

Fig. 1. AFM images for (a) BMT and (b) BZT thin lms.

preferential orientations of the thin lms depend on the growth conditions (substrate temperature, oxygen pressure, laser uence, etc.) and on the nature of the substrate [16]. In a previous work [7], strong dependence of the BMT lms texture on the laser uence was evidenced. Therefore, the different crystallization behavior could be attributed to the different laser uence values used for lm deposition. The BXT bulk ceramics exhibit the complex perovskite struc ture of the P3m1 space group [5]. In the X-ray diffraction pattern, the (1 0 0) peak at 2 17.7 shows the strongest intensity of the superstructure reection peaks [1]. On one hand, the XRD investigations of the BXT targets, sintered at 1650 C for 4 hs, revealed a well-crystallized perovskite phase with a 1:2 long range ordering of X and Ta cations [12,13]. On the other hand, the Ba(X1/3 Ta2/3 )O3

3. Results and discussion The morphologic features of the BXT thin lms grown on Ptcoated Si substrate at 700 C by RF-PLD are presented in Fig. 1a) and Fig. 1b), respectively. There are different surface features for BMT and BZT thin lms, but the roughness values are similar, around RMS 10 nm, which is rather good value for the PLD technique. The X-ray diffraction patterns of the BXT lms are given in Fig. 2. Both lms exhibit a polycrystalline cubic perovskite structure with all peaks assigned to the Pm3m space group. In the detection limit of the method, the BXT lms do not have secondary phases. As it can be seen in Fig. 2, the BMT lm exhibit a strong preferential orientation along (2 0 0) direction. On the other hand, an accentuated preferential growth along (1 1 0) direction was evidenced for BZT thin lms. The lms texture is a consequence of the highly textured (1 1 1) platinum layer. Typically for the PLD method, the

Fig. 2. X-ray diffraction patterns of the BMT and BZT thin lms.

Please cite this article in press as: L. Nedelcu, et al., Structural and dielectric properties of Ba(X1/3 Ta2/3 )O3 thin lms grown by RF-PLD, Appl. Surf. Sci. (2012), http://dx.doi.org/10.1016/j.apsusc.2012.10.124

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L. Nedelcu et al. / Applied Surface Science xxx (2012) xxxxxx 3 Mean crystallite size (nm) 40 65

Table 1 Unit cell constant and mean crystallite size of BMT and BZT thin lms calculated from XRD patterns. Sample BMT BZT Unit cell constant (nm) 0.4096 0.4109

lms show a (disordered) cubic perovskite structure (space group Pm3m). No superstructure reections were observed BXT lms grown by RF-PLD, which could be explained by the relatively lower growth temperature (700 C). Similar to these results, the XRD patterns of the as-grown BXT thin lms reported [711] possess the characteristics of the cubic perovskite structure. However, it was shown that partially ordered BMT thin lms can be obtained after annealing at 1100 C [17]. Therefore, it can be supposed that the ordered BXT thin lms can be obtained after post-annealing at temperature higher than 1100 C, but this high temperature could be a limitation for industrial applications. The unit cell constant and mean crystallite size of BZT and BMT thin lms are listed in Table 1. The XRD calculations were performed using a Bruker DIFFRACplus BASIC Evaluation Package v.12. The mean crystallite size (D) was calculated from the (1 1 0) and (2 0 0) line broadening, respectively, using the Scherrer formula D (nm) = 0.9 (nm) cos (1)

Fig. 4. Temperature behavior of the dielectric constant and lms.

for BMT and BZT thin

where is the full width at half maximum and is the Bragg angle. The line width was corrected for the instrumental broadening using the above mentioned reference sample. The X-ray calculated data for unit cell and constant mean crystallite size of BMT and BZT thin lms are presented in Table 1. The microstructure of BXT thin lms was investigated by using scanning electron microscopy. The cross-sectional SEM micrographs of the fractured surface show that the lms have a columnar microstructure, which is oriented perpendicular to the substrate. Moreover, the SEM images show a continuous smooth interface between the lm and the Pt layer. For instance, in Fig. 3 is presented the SEM micrograph on the cleaved surface of BMT thin lm. From SEM images the thickness of BMT and BZT lms was estimated at 250 nm and 380 nm, respectively. These differences in lm thickness are due to different optical properties (absorption coefcients [18]) and relative density values of the targets (96% for BMT and 94% for BZT).

In order to investigate the dielectric properties of the grown lms, circular gold patches of 0.2 mm2 area were deposited on the top of the BXT lms using DC sputtering through a shadow mask. The measurements were performed at 100 kHz on the obtained metal-insulator-metal capacitors in the 50 to +100 C temperature range. The measured data are shown in Fig. 4. The parallel plate capacitor formula was used for estimation of the relative dielectric permittivity r and temperature coefcient of the dielectric permittivity dened by

1 T

(2)

Fig. 3. SEM image on the cleaved cross-section surface of a BMT thin lm grown on Pt-coated silicon substrate (Si/SiO2 /TiO2 /Pt).

where is the variation in the dielectric permittivity for a T temperature variation The gives information on the temperature stability of the dielectric permittivity and the values inserted in Fig. 4 were calculated by tting the measured r . The expansion coefcient for BXT bulk ceramics is about 10 ppm/ C [1]. Due to the fact that the lm thermal expansion gives a small inuence on , it was neglected for estimation. The dielectric constant (r ) of the BMT lm grown shows a parabolic variation with respect to the temperature in the 50 to +100 C range. On the other hand, a linear change of the r in the whole temperature range was found for the BZT lm. Opposite to the bulk materials [13,19], BXT thin lms possess relatively high positive values of . Investigations on BZT thin lms showed that the temperature behavior of the dielectric constant is strongly inuenced by the degree of crystallization [10]. In was found that the increase in degree of crystallization induces a decrease of one order of magnitude simultaneously with changes in temperature dependence of the dielectric permittivity from a parabolic law to a linear one. Therefore, it can be suppose that the discrepancy in temperature dependence of permittivity for BXT lms is due to extrinsic contributions. These results are in good agreement with the X-ray calculated data for mean crystallite size of BXT samples (Table 1), which indicates an increased degree of crystallization for BZT lms. The temperature dependence of the dielectric loss tan of BXT thin lms is shown in Fig. 5. The thin lms exhibit dielectric losses much higher than the BXT bulk materials, for which tan 104 to 103 [1,19,20]. For bulk material, the BMT exhibits dielectric loss two-three times less than BZT. Despite of that, the BMT and BZT thin lms present similar dielectric loss. On one side, the increase of the dielectric loss with the temperature increase is an evidence of the sample conductivity [21], hence, the high dielectric loss could be explained by the development of

Please cite this article in press as: L. Nedelcu, et al., Structural and dielectric properties of Ba(X1/3 Ta2/3 )O3 thin lms grown by RF-PLD, Appl. Surf. Sci. (2012), http://dx.doi.org/10.1016/j.apsusc.2012.10.124

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Fig. 5. Dielectric loss versus temperature for BMT and BZT thin lms.

structural defects during the lm deposition. On the other side, the difference in dielectric loss between the bulk and thin lm could be the associated to the cubic (disordered) structure of the thin lms in opposition with the hexagonal (ordered) structure of the bulk samples. This issue will be subject of further investigations. 4. Conclusions The BXT thin lms grown on Pt-coated silicon substrates by using RF assisted PLD show a small surface roughness (10 nm). They exhibit a cubic perovskite structure and do not present secondary phases. The lms are highly textured, the BZT and BMT lm presenting a strong preferential orientation along (1 1 0) and (2 0 0) direction, respectively. There is a continuous smooth interface between the lm and the Pt layer. The thin lms show some dielectric properties, which are different from bulk materials. They possess high positive values of , while for bulk BXT materials is negative. Moreover, the BMT and BZT thin lms exhibit dielectric loss of the same order of magnitude, much higher than for the BMT or BZT bulk materials. More investigations are required for a complete understanding of these characteristics. The measured properties of the deposited BXT thin lms make them promising candidates for microelectronic applications. Acknowledgements This work was supported by a grant of the Romanian National Authority for Scientic Research, CNCS-UEFISCDI, project number PN-II-RU-PD-2011-3-0237.

Please cite this article in press as: L. Nedelcu, et al., Structural and dielectric properties of Ba(X1/3 Ta2/3 )O3 thin lms grown by RF-PLD, Appl. Surf. Sci. (2012), http://dx.doi.org/10.1016/j.apsusc.2012.10.124

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