Vacuum 83 (2009) 10181021

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Dielectric properties of (Ba,Ca)(Zr,Ti)O3/CaRuO3 heterostructure thin lms prepared by pulsed laser deposition
L.L. Jiang a, X.G. Tang b, *, Q. Li b, H.L.W. Chan c
a

Laboratory Teaching Center, Guangdong University of Technology, Guangzhou Higher Education Mega Center, Guangzhou 510006, Peoples Republic of China School of Physics and Optoelectric Engineering, Guangdong University of Technology, Guangzhou Higher Education Mega Center, Guangzhou 510006, Peoples Republic of China c Department of Applied Physics, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, Peoples Republic of China
b

a r t i c l e i n f o
Article history: Received 9 June 2008 Received in revised form 1 November 2008 Accepted 4 November 2008 PACS: 77.50f 77.80.Dj 77.22.d Keywords: Dielectric properties Barium calcium zirconate titanate Heterostructure BCZT/CRO Thin lms Tunability Pulsed laser deposition

a b s t r a c t
(Ba0.90Ca0.10)(Zr0.25Ti0.75)O3 (BCZT) thin lms were grown on Pt/Ti/SiO2/Si substrates without and with a CaRuO3 (CRO) buffer layer using pulsed laser deposition (PLD). The structure and surface morphology of the lms have been characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). At room temperature and 1 MHz, the dependence of dielectric constant and tunability of the lms with electric eld were investigated; the dielectric constant and tunability are 725 and 47.0%, 877 and 50.4%, respectively, for the BCZT lm on Pt/Ti/SiO2/Si substrates without and with the CRO buffer layer at 400 kV/cm. The tunability of the BCZT/CRO heterostructure thin lms on Pt/Ti/SiO2/Si substrates was higher than that of the BCZT thin lms on Pt/Ti/SiO2/Si substrates. The high constant likely results from the oxide electrode (CRO). 2008 Elsevier Ltd. All rights reserved.

1. Introduction Barium strontium titanate (Ba,Sr)TiO3 (BST) thin lms have currently become very attractive for applications in decoupling capacitors, storage capacitors, and dielectric eld tunable elements for high frequency devices [13]. The high dielectric constant and low loss make BST one of the most promising candidates for DRAM and tunable microwave device applications. The large electrical eld-dependent dielectric constant can be used for devices such as tunable oscillators, lters and phase shifters. In such devices, it is desirable to have a high dielectric tunability in a certain electric eld range as well as low dielectric loss. The solid solution behavior of Ba(ZryTi1 y)O3 suggests this composition as an alternative to BST in the fabrication of ceramic capacitors because Zr4 is chemically more stable than Ti4 [48]. Solid solution of barium titanate BaTiO3 and barium zirconate BaZrO3, Ba(ZryTi1 y)O3 (BZT), have similarities to BST solid solutions [4,5]. The mixed titanium/zirconium composition generates cation site disorder on the 4 cation

* Corresponding author. Fax: 86 20 3932 2265. E-mail address: xgtang6@yahoo.com (X.G. Tang). 0042-207X/$ see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.vacuum.2008.11.001

lattice sites thereby inducing residual lattice strain. The nature of the ferroelectric phase transition at the Curie temperature (TC) of BZT bulk ceramics is known to change strongly with the Zr content. At higher Zr contents (y > 0.08), BZT bulk ceramics show a broad dielectric constant-temperature (3wT) curve near TC, which is caused by inhomogeneous distribution of Zr ions in Ti sites and mechanical stress in the grain. This can be considered as a result of pinch-off of the three phase transitions of pure BaTiO3 at high Zr concentration (y ! 0.15) [6]. As the Zr content increases, the phase transition temperatures approach each other, until, at a Zr content of y w 0.20, only one phase transition exists [7]. Below this temperature, the rhombohedral phase is stable; above this temperature, the cubic phase is stable [8]. The related system of (Ba,Ca)(Zr,Ti)O3 ceramics are reported to exhibit a broad dielectric constant-temperature curve near TC, with values as high as 3 w18,000 [9]. The calcium doped barium titanate has a characteristic of diffuse phase transition [10]. While it is known that the dielectric constant of (Ba,Ca)(Zr,Ti)O3 ceramics is high [9], we only recently reported the eld dependence of dielectric constant of (Ba0.90Ca0.10)(Zr0.25Ti0.75)O3 ceramics [11]. Not much work has been performed on the dielectric properties and tunabilities of (Ba,Ca)(Zr,Ti)O3 thin lms. The fabrication of

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(Ba0.96Ca0.04)(Ti0.84Zr0.16)O3 thin lms by radio frequency magnetron sputtering [12], and by the metalorganic decomposition method [13,14], and their respective dielectric properties have been reported recently. In comparison with related lms formed by metalorganic decomposition of (Ba0.96Ca0.04)(Ti0.84Zr0.16)O3 on Ptcoated substrates has a high dielectric constant of 460 at 1 MHz [13]. Many efforts have been made to improve the dielectric properties of BST thin lm capacitors, including using conductive oxide electrodes such as (La0.7Ca0.3)MnO3 [14], (La0.5Sr0.5)CoO3 [15], (Ba,Sr)RuO3 [16], LaNiO3 [17] YBa2Cu3O7 (YBCO) [18] and CaRuO3 [19]. The effects of a CaRuO3 bottom electrode on the dielectric properties and tunability of (Ba,Ca)(Zr,Ti)O3 lms has not yet been reported. In our previous work, (Ba0.90Ca0.10)(Zr0.25Ti0.75)O3 ceramics with high tunability and gure-of-merit [11]. In this work, (Ba0.90Ca0.10)(Zr0.25Ti0.75)O3 thin lms grown on Pt(111)/Ti/SiO2/ Si(100) substrates without and with a CaRuO3 buffer layer were prepared by pulsed laser deposition. The dielectric properties and tunability of the (Ba0.90Ca0.10)(Zr0.25Ti0.75)O3 thin lms on Pt/Ti/ SiO2/Si substrates without and with a CaRuO3 bottom electrode are also reported. 2. Experiment CaRuO3 (CRO) bottom electrode layer was grown on Pt/Ti/SiO2/ Si substrates at 750  C by rf-magnetron sputtering using a CRO target [19]. The (Ba0.90Ca0.10)(Zr0.25Ti0.75)O3 (BCZT) thin lms were grown on Pt/Ti/SiO2/Si substrates kept at 650  C by pulsed laser deposition (PLD) using a KrF eximer pulsed laser (l 248 nm), and BCZT and CaRuO3 targets. These BCZT target was prepared by a sol gel process [11], and also a conventional solid state reaction, respectively. The lms were deposited at a laser repetition rate of 10 Hz and a laser energy of 300 mJ/pulse. The base pressure of the system is 2 mTorr. The laser energy density on rotating targets of BCZT was 2 J/cm2. The target-substrate distance was 45 mm. The deposition time is 25 min for the BCZT lm. And the deposition rate was 20 nm/min. The oxygen pressure was an important parameter and was kept at 200 mTorr. Finally, the bottom electrodes were crystallized in situ at 650  C in 400 mTorr of oxygen for 10 min and cooled down slowly to room temperature for fabrication of electrode. Similarly, BCZT thin lms were crystallized in situ at 650  C in 400 mTorr of oxygen for 10 min and cooled down slowly to room temperature to produce a random oriented BCZT/CRO heterostructure. Details of the deposition conditions are given in Table 1 and Ref. [20]. The thickness of the as-grown thin lms on Pt/Ti/ SiO2/Si substrates was measured by a Tencor P-10 surface proler (KLA-Tenor Corporation, USA). Thickness of the bottom electrode layer is 20 nm. The thickness of BCZT thin lms on Pt/Ti/SiO2/Si and on CRO/Pt/Ti/SiO2/Si substrates were about 500, and 500 nm, respectively. The crystalline structure of BCZT thin lms on Pt/Ti/SiO2/Si substrates was examined using X-ray diffractometer (Philips PW3710) with Cu Ka radiation. The thickness and cross-sectional

microstructure were determined by scanning electron microscopy ((SEM), Leica Stereoscan 440). For electrical measurements of a thin lm capacitor, top gold (Au) electrodes of 0.2 mm diameter were deposited through a shadow mask onto the BCZT thin lms by pulsed laser deposition. The dielectric properties of Au/BCZT/Pt and Au/BCZT/CRO/Pt capacitors were measured using an Agilent 4294A impedance analyzer at room temperature. All measurements were performed as cycle sweeps (zero voltage to positive voltage back to zero voltage, zero voltage to negative voltage back to zero voltage) to check for any possible hysteresis. 3. Results and discussion Fig. 1 shows the X-ray diffraction (XRD) pattern of the BCZT thin lms deposited on Pt/Ti/SiO2/Si substrates without and with a CRO buffer layer, respectively, that had been crystallized in situ at 650  C for 10 min in oxygen atmosphere. Four peaks (100), (110), (200), and (211) were observed in the XRD patterns of the BCZT/Pt and BCZT/CRO heterostructure thin lms. BCZT lms deposited on Pt/Ti/ SiO2/Si substrates without and with CRO buffer layer, are polycrystalline with random orientation (see Fig. 1(a) and (b)). Fig. 2 shows surface and cross-sectional SEM images of the BCZT thin lms on Pt/Ti/SiO2/Si substrates. In Fig. 2, the thin lms show homogenous and uniform microstructures. As seen in Fig. 2(a) and (b), many clusters are found on the surface image of BCZT/Pt thin lms, which are composed of nano-sized grains of 80w150 nm. The cross-sectional image of BCZT/Pt thin lms exhibits a columnar growth morphology characteristic of the grains, and the grain size is about 120 nm. From the SEM images, it is seen that the BCZT thin lms are smooth. The BCZT/Pt thin lms thickness from these images and from surface proling measurements is 500 nm. The dielectric constant and dielectric loss (tan d) were measured by applying a small ac signal of 0.5 V amplitude as a function of frequency in the range of 100 Hz1 MHz. Fig. 3(a) and (b) show the frequency dependence of the dielectric constant and loss tan d for the BCZT thin lms on Pt/Ti/SiO2/Si substrates without and with a CRO lm, both the dielectric constant and loss tan d decrease from 922 and 0.036 to 725 and 0.023 with increasing frequency from 100 Hz to 1 MHz. For the BCZT/CRO/Pt/Ti/SiO2/Si lm structure, the dielectric constant and loss tan d decreases from 1371 and 0.042 to 877 and 0.025 with increasing frequency from 100 Hz to 1 MHz. The dielectric loss slightly increase and then decrease when the

(a) BCZT/CRO/Pt (b) BCZT/Pt

Intensity (arb.units)

(110)

(100)

Deposition parameters Deposition method Deposition temperature Film thickness Base vacuum Energy (power) used Repetition rate Deposition time Working pressure Annealing temperature Substrates

(Ba0.90Ca0.10)(Ti0.75Zr0.25)O3 PLD 650  C 500 nm 2 106 Torr 300 mJ/pulse 10 Hz 25 min 200 106 Torr 650  C CRO/Pt/Ti/SiO2/Si

(b)

(a)
20 30

Pt(111)

CRO

40

(200)

50

(211) 60

Table 1 Deposition conditions of BCZT thin lms by PLD.

Fig. 1. XRD patterns of (a) BCZT/CRO/Pt, and (b) BCZT/Pt.

PtK

2 (deg)

1020

L.L. Jiang et al. / Vacuum 83 (2009) 10181021

Fig. 2. (a) Surface and (b) cross-sectional SEM images of BCZT lms on Pt/Ti/SiO2/Si substrates.

buffer layer is present, the reason was space charge relaxations related to conductivity layer. At 100 kHz, the dielectric constant and dissipation factor are 770 and 0.022, and 929 and 0.023, respectively for the BCZT thin lms on Pt/Ti/SiO2/Si substrates without and with a CRO buffer layer. Dielectric constants of pulsed laser deposition BCZT lms were higher than those of radio frequency magnetron sputtered and CVD-decomposited BCZT lms (3r 166w460) [12,13]. The dielectric constant is enhanced in the presence of a CRO buffer layer. The dc bias eld dependence of both dielectric constant and dielectric loss at room temperature (25  C) was measured to evaluate the dielectric tunabilities of the BCZT lm on Pt/Ti/SiO2/Si and BCZT heterostructure thin lms on Pt/Ti/SiO2/Si substrates. The measurements were conducted by applying a small ac signal of 0.05 V amplitude and 1 MHz frequency while the dc eld was swept from positive bias to negative bias. The potential of the BCZT lms to be used in voltage-tunable devices depends on the ability to change the dielectric constant by means of an applied electric eld. The electric eld dependence of the dielectric constant (3r) and loss (tan d) at room temperature is shown in Fig. 4. As expected, a slight hysteresis was observed in these characteristics, as a result of the existence of ferroelectric domains at room temperature. The dielectric tunability, in percent is dened in terms of DC/C0, where DC is the change in capacitance relative to the zero-bias capacitance C0 [21]. For BCZT thin lms intended for electrically tuned device applications the interaction between the dielectric loss and tunability is usually given by a gure-of-merit, K, is dened as K tunability/tan d (DC/C0)/tan d [1]. The tunability and K values of BCZT thin lms on Pt/Ti/SiO2/Si substrates without and with a CRO buffer layer were 47.0% and 20.4, 50.4% and 20.1 respectively at an applied eld of 400 kV/cm. It has been proposed that the reduction of 3r in ferroelectric thin lms can be explained by the existence of an interfacial dead layer at one or both metal electrodes that exhibit poor dielectric properties [2,22,23]. It may arise from oxygen interdiffusion, interfacial chemical reaction, structural defects, or a Schottky barrier at the interfaces. The inverse capacitances density of such Au/BCZT/Pt multilayer is expressed by Eq. (1):

A C

d 2di

3r 30
1000

2di

3i 30

(1)

1500

(a) BCZT Film (b) BCZT/CRO Film

0.20

900 0.16 800

(a) BCZT/Pt, Tunability=47.0% (b) BCZT/CRO, Tunability=50.4%

Dielectric constant

1000 0.12

Dielectric constant

700

Loss tan

0.08 500 0.04

600

500

400 0 102 0.00 106

103

104

105

300

-400

-200

200

400

Frequency (Hz)
Fig. 3. Frequency dependence of dielectric constant and loss tan d of BCZT thin lm on Pt/Ti/SiO2/Si substrates: (a) without and (b) with a CRO buffer layer.

Electric Field (kV/cm)

Fig. 4. Electric eld dependence of dielectric constant and loss tan d of BCZT thin lm on Pt/Ti/SiO2/Si substrates: (a) without and (b) with a CRO buffer layer.

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where A is the capacitor area, C is the capacitance, d is the thickness of the measured lm, di is the thickness of the nonbulk-like interfacial layer, 3r,3i, and 3o are the bulk permittivity values associated with the interior, lm surface, and free space, respectively. These equations have been widely used to model thickness dependent dielectric properties [2224]. From Eq. (1), 3r decreased with a decrease 3i. Experimental verication has been demonstrated by Lee and Hwang [23] and Parker et al.[24]. In the Pt/BST/Pt system, the decrease in 3r with decrease in lm thickness is due to the existence of an interfacial dead layer at the Pt/BST surface. However, for the Pt/BCZT/CRO capacitor, the inuence of two interfaces (Pt/BCZT and BCZT/CRO) on the dielectric properties is actually quite different. As discussed by Vendik et al. [25], the polarization of a dielectric layer can penetrate into the oxide electrodes, meaning that the dielectric/oxide interface can be characterized by free-boundary conditions. In other words, the inuence of the ferroelectric/oxide interface can be eliminated and there would be no signicant thickness dependence in an oxide/BST/ oxide heterostructure. These assertions have been experimentally veried by Hwang [26] and Dittmann et al. [27] for the IrO2/BST/ IrO2 and SrRuO3/BST/SrRuO3 heterostructures. The decrease in the measured dielectric constant of BST thin lms having Pt electrodes with decreasing dielectric lm thickness is in response to the nite charge-screening length of the metal electrode and the intrinsicdead layer of the dielectric interface. On the other hand, the nearly lm-thickness-independent dielectric constant of the BST thin lms with conducting oxide electrodes, IrO2 and SrRuO3, was attributed to the very high capacitance values of the chargescreening layer of the oxide electrodes. The very high capacitance value appeared to originate from the strain-induced high dielectric constant of the oxide electrodes [26]. Use of conductive oxide electrodes, such as LSMO, CaRuO3, LaNiO3, and YBCO, can decrease the thickness of the dead layer [2628], and enhance the dielectric constant and tunability [2,1418,2628]. Hence, Pt/BCZT/CRO capacitors have higher dielectric constant and tunability. The very high capacitance value appeared to originate from the straininduced high dielectric constant of the oxide electrodes [26]. 4. Conclusions In conclusion, (110)-oriented BCZT thin lms have been deposited on Pt/Ti/SiO2/Si substrates without and with a CRO buffer layer by pulsed laser deposition. For BCZT thin lms on Pt/Ti/SiO2/Si substrates, the average grain sizes were about 120 nm. At room temperature and a frequency of 1 MHz, the dependence of dielectric constant and tunability of the lms on the electric eld were investigated; the dielectric constant and tunability are 725 and

47.0%, and 877 and 50.4%, respectively for the BCZT lm on Pt/Ti/ SiO2/Si substrates without and a CRO buffer layer at 400 kV/cm. The dielectric constant and tunability of the BCZT/CRO heterostructure thin lm on a Pt/Ti/SiO2/Si substrates was higher than that of the BCZT thin lm on Pt/Ti/SiO2/Si substrates. This larger value has been attributed to the presence of the CRO electrodes. The BCZT thin lm is an attractive candidate for tunable microwave device applications. Acknowledgements This work is supported by the National Natural Science Foundation of China (Grand No. 10774030), and the Guangdong Provincial Natural Science Foundation of China (Grant No. 8151009001000003). References
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