Journal of the Korean Physical Society, Vol. 57, No. 4, October 2010, pp.

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Eects of Starting Powder on the Growth of Al2 O3 Films on Cu Substrates Using the Aerosol Deposition Method
Dong-Won Lee, Hyung-Jun Kim and Song-Min Nam
Department of Electronic Materials Engineering, Kwangwoon University, Seoul 139-701, Korea (Received 2 February 2010, in nal form 31 August 2010) The origin of craters on the surfaces of aerosol deposited ceramic thick lms has been ascribed to the mechanical impact of large and hard ceramic particles; however, the main cause of craters has not been fully claried. To determine the fundamental cause of the craters, three types of -Al2 O3 powders, with particles of dierent sizes and shapes, were prepared; Al2 O3 thick lms were deposited on Cu substrates using these powders, and aspects of deposition were observed. The surfaces of the aerosol-deposited Al2 O3 lms showed considerably dierent morphologies, depending on the starting powder. In the case of large and agglomerated Al2 O3 starting powders, the surface roughness of the deposited lms increased and the deposition rate decreased compared with that of standard Al2 O3 powder having particles with an average size of 0.5-m. In addition, we conrmed an increase in the crater size when using the large and agglomerated particles. For Al2 O3 starting powder with 0.5-m particles, the relative permittivity and loss tangent of the deposited Al2 O3 lms were 9.8 and 0.013, respectively; however, large and agglomerated Al2 O3 powders produced lm with a signicant increase in dielectric loss. As a result, the agglomerated and large particles were conrmed to particles adversely aected the surface morphology and the dielectric properties.
PACS numbers: 73.61.Ng Keywords: Aerosol deposition method, Crater, Al2 O3 , Agglomeration, Cu substrates DOI: 10.3938/jkps.57.1115

I. INTRODUCTION A novel method for fabricating ceramic lms, the aerosol deposition method (ADM), has recently been used in many elds for applications of the piezoelectric devices, such as micro-electromechanical systems (MEMS), optical scanners and ink jet print heads [1 4], and of high-frequency devices, such as embedded capacitors with a multilayer structure, and optical devices [57]. ADM is based on impact adhesion of ne particles and is an attractive coating method for these applications because it aords high-speed deposition, is a room temperature processing, and can achieve ne patterning in a ceramic coating [810] compared with conventional thin-lm methods and thermal spray coating technology [11,12]. However, the surface of aerosol-deposited ceramic lms can be rough due to craters [13,14]. These rough surfaces degrade the device performance. For example, in optical devices, rough surfaces signicantly degrade the reectance, transmission, and scattering loss of optical components due to increased scattering. In highfrequency devices, the rough surfaces increase the trans E-mail:

smnam@kw.ac.kr; Tel: +82-2-940-5764; Fax:+82-2-942-

mission loss at interface regions between the ceramic and metal interconnects due to signal attenuation and dispersion of the interfaces. This transmission loss results in a disturbance of the current ow in the conductor, which is especially noticeable at higher frequencies [15,16]. Previous studies reported that the rough surfaces of ceramic lms are due to surface relief features, such as craters, but the fundamental causes of the craters have not been claried [5,13]. Through recent observations of the surface morphologies from the initial growth stages to the nal thick lms, the main cause of cratering of aerosol-deposited Al2 O3 lms was investigated, and explained as due to the impact of hard and large Al2 O3 particleslarger than 1 m; the surfaces are much rougher compared to the surface morphologies of aerosoldeposited Ag or polyimide lms. In addition, an increase in the diameter of craters with the growth of Al2 O3 lms was revealed by analysis of rms roughness and observation of surface microstructures, which increase resulted in a deterioration of the surface roughness of the Al2 O3 lms [17]. In this study, to validate the conclusions about the main cause of crater generation, we prepared three types of starting Al2 O3 particles with dierent sizes and shapes and investigated the powder dependence of the surface morphologies of Al2 O3 thick lms deposited on at Cu

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substrates. Through observation of the surface morphology and evaluation of the crystallinity, as well as measurements of the surface roughness and thickness, a comparative study of Al2 O3 thick lms formed by using the three types of Al2 O3 particles was attempted and the dielectric properties of the Al2 O3 thick lms made with these starting powders were evaluated.

II. EXPERIMENTS Using ADM, Al2 O3 lms were deposited on at Cu substrates at room temperature. The details of the ADM apparatus are reported elsewhere [1,18]. Three types of -Al2 O3 particles were prepared as starting powders. The rst powder used ne -Al2 O3 particles-0.5-m in average diameter, with a purity of 99.8% (Showa Denko Co., Ltd.) and AL-160SG3. The second type used Al2 O3 particles with an average diameter of 3 m and purity of 99.9% (Showa Denko Co., Ltd.) and AES-43. The third type used -Al2 O3 particles with agglomerated shapes and a purity of 99.99% (Rare-metallic Co., Ltd.). In the aerosol chamber, the Al2 O3 particles were made into an aerosol by the vibration and mixing system. The particles were dispersed by vibration into a helium carrier gas and accelerated through a nozzle. The aerosolized Al2 O3 particles strike the at Cu substrate and form a dense lm at room temperature. The particle size distribution of the three types of -Al2 O3 particles was measured with a particle size analyzer (PSA). To obtain Al2 O3 lms with a uniform thickness, the Cu substrates were continuously scanned along the nozzle at a velocity of 1.5 mm/s; the deposition area was 5 10 mm2 . The microstructures and the crystallinity of the Al2 O3 thick lms were examined by using eldemission scanning electron microscopy (FE-SEM) and Xray diraction (XRD) analysis, respectively. The dielectric properties were measured from 100 Hz to 10 MHz using an impedance analyzer (HP4194A). For this measurement, gold upper electrodes, 1.0 mm in diameter, were coated on by sputtering. The surface morphologies and thicknesses of the Al2 O3 thick lm layers were measured by an atomic microscope (AFM) and a surface prolometer, respectively.

Fig. 1. SEM images of (a) 0.5-m Al2 O3 powder, (b) large Al2 O3 powder, and (c) agglomerated Al2 O3 powder. PSA results of (d) 0.5-m Al2 O3 powder, (e) large Al2 O3 powder, and (f) agglomerated Al2 O3 powder.

III. RESULTS AND DISCUSSION To support the results concerning the main cause of the craters that degrade the surface roughness of Al2 O3 lms, three types of Al2 O3 starting powder were prepared [17]. Figure 1 shows SEM images and PSA results of the dierent Al2 O3 starting powders. The rst starting powder used 0.5-m Al2 O3 particles, as shown in Fig. 1(a). In Fig. 1(d), the particle size is broadly distributed in the range of 0.1 to 2 m, and there are

many 1 m Al2 O3 particles. The second type of starting powder used Al2 O3 particles larger than 3 m, as shown in Fig. 1(b). The third type of Al2 O3 starting powder used severely agglomerated Al2 O3 particles, as shown in Fig. 1(c); the particle sizes were broadly distributed in the range from 1 to 30 m. XRD patterns of the Al2 O3 starting powders revealed that all three have a single Al2 O3 phase. These three types of -Al2 O3 particles, with dierent sizes and shapes, were deposited on at Cu substrates by using the ADM under the same experimental conditions. Figure 2(a) shows the surface morphologies when using 0.5-m Al2 O3 particles. The surfaces show surface reliefs, such as craters, and the sizes of craters are approximately 1 m. These are caused by the mechanical impact of large and hard Al2 O3 particles larger than 1 m. Higher SEM magnication showed 10 nm Al2 O3 particles present in the lms, which resulted in the cracking of 0.5-m Al2 O3 particles. Tilted-SEM images conrmed very dense thick lms. The rms roughness was approximately 116 nm, and the lm thickness about 20 m. On the other hand, when using large particles, larger than 3 m, very large craters were observed in lms, as shown in Fig. 2(b). The Al2 O3 lm surface deteriorated, with a rms roughness of 654 nm, and the thickness was reduced to 8 m. It is thought that the kinetic energy is too high to be deposited due to the big mass of large particles. Moreover, at higher SEM magnication, it was observed

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Fig. 2. Plane-view SEM images of Al2 O3 thick lms aerosol deposited by using (a) 0.5-m Al2 O3 powder, (b) large Al2 O3 powder, and (c) agglomerated Al2 O3 powder. Tilted SEM images of Al2 O3 thick lms aerosol deposited by using (d) 0.5-m Al2 O3 powder, (e) large Al2 O3 powder, and (f) agglomerated Al2 O3 powder.

Fig. 3. X-ray diraction patterns of Al2 O3 thick lms aerosol deposited using (a) agglomerated Al2 O3 powder, (b) large Al2 O3 powder, and (c) 0.5-m Al2 O3 powder.

that there were 10 and 100 nm Al2 O3 particles, as well as large craters, which were made by the impact of large particles. When using agglomerated Al2 O3 particles, the rms roughness of Al2 O3 lms increased considerably-to 958 nm. Here, we can observe very rough surfaces due to the deep craters; the diameter of these craters is larger than that shown in Fig. 2(a). The thickness of the lms was approximately 7 m. These results revealed that the size and shape of the particles have a great inuence on both the thickness and surface roughness of Al2 O3 lms. This means that large and agglomerated particles do serious damage to lms rather than contribute to their growth. Next, the crystal structures of the Al2 O3 lms were investigated to determine the relationship between microstructure and a crystallite size. Figure 3 shows Xray diraction patterns of Al2 O3 thick lms aerosoldeposited using the three types of Al2 O3 starting powder. This shows that a single -Al2 O3 phase exists without any second phases, despite being deposited at room temperature, which means that the Al2 O3 crystallinity is retained throughout the ADM process. Figure 3(c) shows XRD patterns of Al2 O3 thick lms grown using 0.5-m Al2 O3 powders. Figures 3(a) and (b) show XRD patterns of Al2 O3 thick lms grown using agglomerated Al2 O3 powders and large Al2 O3 powders, respectively. The XRD patterns conrm that the -Al2 O3 peaks of

Fig. 4. Correlation between the rms roughness and the deposition rate of Al2 O3 lms with the three types of starting powders.

Fig. 3(a) broadened in comparison with those of Figs. 3(b) and (c). This peak broadening was caused by residual stress and small crystallite size. Also, it is believed that these phenomena are caused by the impact of substrate with particles or particles with particles and the subsequent fracturing of particles. To support this, the crystallite sizes of the 116 diraction peaks of Al2 O3 are calculated by Scherrers method. In Fig. 3(c), the crystallite sizes of the 116 diraction peaks of Al2 O3 were approximately 11 nm, which corresponds with the microstructure of Al2 O3 lms with 10-nm-order-sized particles, as shown in Fig. 2(a). On the other hand, when us-

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Fig. 5. (Color online) Roughness proles along selected lines in AFM topography of the Al2 O3 lms deposited by using (a) 0.5-m Al2 O3 powder, (b) large Al2 O3 powder, and (c) agglomerated Al2 O3 powder.

ing large and agglomerated Al2 O3 particles, the crystallite sizes of the 116 diraction peaks of Al2 O3 increased to approximately 17 nm and 13 nm, respectively. The increase in these crystallite sizes is explained by observation of the microstructures. The high magnication images in Figs. 2(b) and (c) show the presence of both 10 and 100 nm particles, which means that large or agglomerated particles are cracked into 10 and 100 nm sizes by bombardment. These large or agglomerated particles are not thought to contribute additional kinetic energy for bonding because their kinetic energy is too high-they make craters in the lm and thereby deteriorate the lm surface. To further understand these results, we investigated the correlation between the deposition rate and the rms roughness with the three types of starting powders, as shown in Fig. 4. When using 0.5-m Al2 O3 particles, the deposition rate increased to 2 m/min, while the rms roughness decreased considerably; however, when using large and agglomerated particles, the deposition rate was signicantly reduced, combined with a sharp increase in rms roughness. This means that the starting particles play an important role in determining lms during ADM. To compare the roughness proles of the three types of Al2 O3 lms, the surface morphologies of these lms were investigated using AFM. Figure 5 shows 10 10 m images of Al2 O3 lms with the topographic proles, where the surface roughness is observed along with the formation of craters. Figure 5(a) shows craters with a diameter of approximately 1 m and a depth of approximately 200 nm. However, for large particles and agglomerated particles, large craters, with a diameter greater than 2 m and a depth greater than 200 nm, were observed. From these

roughness proles along selected lines in the AFM and the surface morphologies, we learn two facts about the causes of craters: the craters are caused by the impact of Al2 O3 particles larger than 1 m; and, larger starting participles produce larger craters. Therefore, the selection of starting particles with an appropriate size is critical in preparing high quality Al2 O3 thick lms at room temperature with ADM. To obtain more detailed information about the cause of craters, at the initial growth stage, three types of Al2 O3 particles were deposited on at Cu substrates. Figure 6 shows plane-view SEM images of the formation of the three types of Al2 O3 particles, which were moved onto the Cu substrates. In the initial stages for 0.5-m Al2 O3 particles, we observe both plastic-deformed Al2 O3 particles and craters, but plastic-deformed Al2 O3 particles dominate on the Cu substrates. These plastic-deformed Al2 O3 particles look like dough mashed into a wall, and are seen in the upper inset images. For large and agglomerated Al2 O3 particles, in the initial stages, many craters are observed on the Cu substrates. Although some Al2 O3 particles are plastic deformed, most of them dent the Cu substrates because of their high kinetic energy, compared with that of 0.5-m Al2 O3 particles. The upper inset in Figs. 6(b) and (c) clearly conrm that large particles or agglomerated particles get stuck in Cu substrates without plastic deformation-the substrates are severely damaged by the mechanical impact of large and agglomerated Al2 O3 particles. Based on these results, Al2 O3 lms grow well with Al2 O3 particles with a size of approximately 0.5 m, while larger particles, above 1 m, or agglomerated particles, preclude lm growth and roughen the lm surface through cratering.

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Fig. 6. Plane-view SEM images of Al2 O3 particles formed by using (a) 0.5-m Al2 O3 powder, the inset being a tilted SEM image of the plastic-deformed Al2 O3 particles, (b) large Al2 O3 powder, the inset being a tilted SEM image of large particle and (c) agglomerated Al2 O3 powder, the inset being a tilted SEM image of agglomerated Al2 O3 particle.

Fig. 7. (Color online) Relative permittivity and loss tangent of Al2 O3 thick lms aerosol deposited with dierent Al2 O3 starting powders.

Next, the dielectric properties of Al2 O3 thick lms aerosol deposited by using the three types of Al2 O3 powders were measured with an impedance analyzer. As shown in Fig. 7, the relative permittivity and the loss tangent of Al2 O3 thick lms aerosol deposited for 0.5-m Al2 O3 particles were 9.4 and 0.05 at 1 MHz, respectively. This indicates that their dielectric properties are as good as those of Al2 O3 ceramic. For aerosol-deposited Al2 O3 thick lms using large Al2 O3 particles, the relative permittivity and loss tangent were 1.3 and 110 at 1 MHz, respectively; for aerosol-deposited Al2 O3 thick lms with agglomerated Al2 O3 particles, the relative permittivity and loss tangent were 1.3 and 92 at 1 MHz, respectively. We conrmed that aerosol-deposited Al2 O3 thick lms with 0.5-m Al2 O3 particles show better dielectric properties than aerosol-deposited Al2 O3 thick lms using large or agglomerated Al2 O3 particles. However, the frequency dependence of the dielectric properties of aerosol-deposited Al2 O3 thick lms using large and agglomerated Al2 O3 particles increased considerably. This phenomenon is not understood, but it was found that there is an optimum particle size for good dielectric prop-

erties of Al2 O3 thick lms. To consider the relationship of dielectric properties to varying frequency, the magnitude and phase of impedance of aerosol-deposited Al2 O3 thick lms, using the three types of Al2 O3 particles, were measured by impedance analyzer, as shown in Fig. 8. As seen in Fig. 8(a), aerosol-deposited Al2 O3 thick lms made with 0.5-m Al2 O3 particles acted like dielectrics-the phase values of their impedance were approximately -90 . In contrast, for aerosol-deposited Al2 O3 thick lms made with large and agglomerated Al2 O3 particles, the phase values of their impedance increased with the frequency. To explain this phenomenon, two types of equivalent circuits, an R-C parallel circuit and R-C series circuit, were proposed. In the case of an R-C parallel circuit, Rp has generally high values while Cp has small values; however, for the R-C series circuit, Rp has generally small values while Cp has high values. So, as the frequency increases Rp is dominated by the increase in Cp , and the phase values of their impedance increases. As a result, the loss due to the series resistance Rs is more signicant than the leakage loss due to the parallel resistor Rp . Moreover, an R-C series circuit has very high contact resistance in comparison with the R-C parallel circuit. Thus, it was concluded that aerosol-deposited Al2 O3 thick lms with

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IV. CONCLUSION The eect of starting powder on growth of Al2 O3 lms was investigated to determine the main cause of crater generation. Using three types of Al2 O3 particles, with dierent sizes and shapes, -Al2 O3 thick lms were grown on at Cu substrates at room temperature by ADM. The aerosol-deposited Al2 O3 lms had considerably dierent surface morphologies. Large and agglomerated particles produced craters with diameters larger than those with 0.5-m Al2 O3 particles. In addition, both the surface morphology and the deposition rate deteriorated in comparison with Al2 O3 lms formed with 0.5-m Al2 O3 particles. The crystallite size of Al2 O3 lms formed by large particles or agglomerated particles increased over 10 nm, while Al2 O3 lms formed by 0.5m particles had 10 nm crystallite sizes. The relative permittivity and loss tangent of aerosol-deposited Al2 O3 lms formed with 0.5-m Al2 O3 particles were 9.4 and 0.05, respectively; however, for large and agglomerated Al2 O3 particles, the relative permittivity and loss tangent depended on the frequency. Through two types of equivalent circuits and SEM images of the initial stages, we explained that the loss in Al2 O3 lms deposited with large and agglomerated Al2 O3 particles was caused by rough Cu interfaces with high resistance, resulting from the impact of large and agglomerated Al2 O3 particles.

Fig. 8. Impedance and phase with equivalent circuits of thick lms deposited using (a) 0.5-m Al2 O3 powder, (b) large Al2 O3 powder, and (c) agglomerated Al2 O3 powder.

ACKNOWLEDGMENTS This research was supported by a grant from the Fundamental R&D Program for Core Technology of Materials funded by the Ministry of Commerce, Knowledge and Economy, Republic of Korea.

0.5-m Al2 O3 particles acts like a R-C parallel circuit, while those made with large and agglomerated Al2 O3 particles act like a R-C series circuit. To elucidate the above results, we focused on the interfaces between the Cu substrates and Al2 O3 thick lms, which were observed through the initial stages of Al2 O3 lm growth, as shown in Fig. 6. Initially, 0.5m Al2 O3 particles are mainly plastic deformed on the Cu substrate, while large and agglomerated Al2 O3 particles form craters in the Cu substrates. The craters formed by the mechanical impact of large and agglomerated Al2 O3 particles severely damage Cu substrates with ductility. It is thought that rough Cu interfaces, damaged by bombardment of large and agglomerated Al2 O3 particles, have higher resistance than those formed by 0.5-m Al2 O3 particles. Therefore, aerosol-deposited Al2 O3 thick lms made with large and agglomerated Al2 O3 particles act like a R-C series circuit, and the loss is increased by rough Cu substrates with high resistance. Consequently, it was conrmed that large and agglomerated particles are the main cause of craters and signicantly aect the deposition rate, surface roughness, and dielectric properties. Thus, fabricating ceramic lms with good performance requires removing these large and agglomerated particles from the ADM process.

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