Surface and Coatings Technology 116119 (1999) 716720 www.elsevier.

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Deposition of aluminium oxide thin lms by reactive magnetron sputtering

K. Koski a,b, *, J. Ho lsa a, P. Juliet b
a University of Turku, Department of Chemistry, Laboratory of Inorganic Chemistry, FIN-20014 Turku, Finland b CEA Grenoble, CEREM-DEM-SGM-LSMM, F-38054 Grenoble, France

Abstract Aluminium oxide thin lms were deposited by direct current (d.c.) reactive magnetron sputtering on glass-slide, silicon wafer, stainless-steel and polycarbonate substrates. The thicknesses of the lms were between 200 nm and 3.0 mm. The deposition was controlled by the target voltage to obtain stoichiometric thin lms with a high deposition rate. The deposition process was studied in terms of target power, IU characteristics of the target, sputtering gas pressure and substrate bias voltage. The lm properties of interest were O/Al ratio, density, nanohardness, intrinsic stress, crystallographic structure and surface roughness. The deposition rate obtained for stress-free and transparent aluminium oxide thin lm was 215 nm min1, 77% of the rate of metallic aluminium. 1999 Elsevier Science S.A. All rights reserved.
Keywords: Aluminium oxide; Deposition rate; Physical properties; Reactive sputtering

1. Introduction Aluminium oxide thin lms are widely used in many mechanical, optical and microelectronical applications because of their excellent properties [1], in terms of chemical inertness, mechanical strength and hardness [2], transparency, high abrasive and corrosion resistance, as well as insulating and optical [3] properties. Poor deposition rate due to target poisoning, hysteresis phenomena, arcing and inhomogeneity are the main disadvantages of the reactive sputtering technique. Controlling the deposition process by target voltage instead of power reduces the target poisoning and hysteresis eects during the process. Arcing can be minimized by using a pulsed power supply and correct choice of the position of the gas injectors

2. Experimental 2.1. Deposition of thin lms The substrate materials used were glass, silicon, stainless steel and polycarbonate. Prior to deposition, the
* Corresponding author. Fax: +33-476-88-51-30. E-mail address: koski@chartreuse.cea.fr ( K. Koski)

substrates were treated chemically in ethanol for 5 to 15 min in an ultrasonic bath to remove organic contaminants. The substrates were not sputter-cleaned. The target was sputtered for 1020 min at 1.0 Pa Ar pressure prior to the lm deposition to remove AlO contamix nants from the target erosion track. The thickness of the aluminium oxide thin lm on the given substrates varied between 200 nm and 3.0 mm. An Alcatel reactive physical vapour deposition (PVD) apparatus was used for the lm deposition. The processing chamber was evacuated by a turbomolecular pump up to a pressure range of 104 Pa prior to the experiments. A 6-inch (15-cm) diameter target of 99.999 at.% Al (manufacturer SenVac GmbH, Germany) was rmly glued to a water-cooled backing plate. A dierentially pumped quadrupole mass spectrometer (Incon Quadrex 100) was connected to the chamber for leak detection, residual gas analysis and deposition control. Ar and O gas ows were controlled with independent 2 ow meters. Argon was introduced in the target housing. Oxygen was introduced in the immediate vicinity of the substrate holder through a home-made circular gas inlet system with 0.5-mm-diameter holes spaced every 10 mm. The diameter of the inlet was tailored to the substrate holder. The distance between the gas inlet and the substrates was 1 or 2 cm from the substrates and 5 cm

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from the target, respectively. The gas inlet reduced the poisoning of the target and improved the oxidation of the lm together with the deposition rate. The argon pressure was varied between 0.30 and 1.0 Pa. The substrate bias voltages were between 0 and 200 V. The target voltage controlled deposition process was used. The voltage was maintained at a constant value. Changes in power during deposition were compensated by decreasing the oxygen gas ow rate to maintain a target power at a nominal value of 10 W. The target voltage and power were between 310 and 405 V and between 1000 and 1500 W (5.58.2 W cm2), respectively. The arc handling was carried out by an Advanced Energy SPARC-LE V Accessory. The passive mode was used to clean the aluminium target and active mode was used during the lm deposition. The frequency was set to 30 kHz, and the reverse voltage used was 15%. 2.2. Characterization of thin lms The thickness and conductivity of the thin lms were measured immediately after the deposition. The thickness was measured with a Taylor-Hobson prolometer using a glass-slide substrate. The lms were transparent when oxidized to stoichiometric aluminium oxide, and black or brown when rich in metal. The lms were observed optically using a microscope and then photographed by a polaroid camera. The lm defects such as craters and droplets on silicon substrate were counted on a surface area of 4.55.75 mm2. A Scanning Electron Microscope (SEM ) by JEOL was used to study the microstructure and surface of the thin lms. A CSEM Atomic Force Microscope (AFM ) was used to image the surface topography of the lm and to detect the surface roughness, R , of the thin lms. a An X-ray diraction ( XRD) facility (Philips PW 1730/1790) was used for crystallographic structure analyses. A Rutherford Backscattering Spectrometer (RBS) ( VAN DE GRAAF accelerator) was used for composition analysis and density measurements. The nanohardness and elastic modulus of the thin lms on Si substrate were measured by nanoidentation with a CSEM Nano Hardness Tester. The residual stress measurements were carried out by recording the curvature of the Si substrate before and after the deposition. The Stoney formula was used to calculate the residual stress of the thin lms.

investigate the inuence of the process parameters on the thin lm properties, one parameter was changed at a time while the others were kept constant. The properties in interest were O/Al ratio, density, nanohardness, surface roughness, morphology, crystallographic structure and intrinsic stress. The target power and the target-to-substrate distance were studied as a function of deposition rate only. The rate increased as a function of target power and targetto-substrate distance. The target power and the targetto-substrate distance varied between 500 and 2000 W, and between 65 and 95 mm, respectively. 3.1. Hysteresis phenomena and deposition rate A typical hysteresis curve for power controlled deposition process is shown in Fig. 1. The target voltage and total pressure were dependent on the oxygen gas ow rate when the target power was kept constant. The target voltage dropped dramatically, and the total gas pressure increased when the oxygen ow rate reached the value of f . By decreasing the gas ow to the value 1 of f , the target voltage increased close to the original 2 value. There exist two target states: metallic and compound modes. The metallic mode of the target indicates high target voltage values and low total gas pressures leading to high deposition rates. The target is at the compound mode when the target voltage is low and the total gas pressure is high. The deposition rate is poor due to poisoned target surface. Arcing is commonly observed during lm deposition when the target is in compound mode. Due to hazardous deposition of aluminium oxide thin lms, the target voltage was used for deposition control. No hysteresis was observed when the deposition process was controlled with a constant target voltage ( Fig. 2). The poweroxygen ow rate curve of the target was the equal when the ow rate of oxygen was increased

3. Results Process parameters have a strong inuence on the thin lm properties and deposition rate. Process parameters in interest were the target voltage, the sputtering gas pressure and the substrate bias voltage. In order to

Fig. 1. Hysteresis response of reactive magnetron sputtering, presented as reactive gas ow ratetarget voltage characteristics.

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Fig. 2. Reactive gas owtarget power characteristics of a voltagecontrolled reactive magnetron sputtering process.

at decreased. The target remained at a constant mode, as chosen by the target voltage. The target modes and deposition rates were controlled by the target voltage (Fig. 3). The target voltages used were between 330 and 440 V. The deposition rate of 215 nm min1 for transparent lm was obtained at a voltage of 405 V. This rate is 77% from the deposition rate of metallic aluminium. Higher target voltage values resulted in brown or black substoichiometric aluminium oxide thin lms. The metallic aluminium was deposited at 440 V. The target power was kept at 150010 W. An important parameter, DU=U (metal )U (deposition), should be taken into account when depositing the aluminium oxide thin lms. The value of U (metal ) depends on the poisoned surface and the area of eroded track of the target, and on the target power. For a highrate deposition process, a DU value between 20 and 60 V was used, depending on the target power. 3.2. Properties of the thin lms deposited It would be ideal to obtain stoichiometric highdensity, stress-free and hard aluminium oxide thin lms with a high deposition rate and excellent adhesion on the substrates. The properties of the thin lms can be

aected by the process parameters and conditions during the deposition. Here, the key parameters are sputtering gas pressure, substrate bias voltage and target voltage. The role of pre-treatment of the substrates is important, too. All the lms deposited had amorphous structure due to a deposition temperature lower than the crystallization temperature of aluminium oxide, 400C. The structure of the lms was columnar. The surface roughnesses of the lms deposited on Si substrates were between 0.72 and 2.64 nm, as measured by AFM. The roughness increased as the sputtering gas pressure increased and the substrate bias voltage decreased. The O/Al ratio of the thin lm depended on the target voltage; low voltages led to superstoichiometric lms, and high voltages led to substoichiometric thin lms. The O/Al ratio was between 1.30 and 1.72. A value of 1.50 was obtained when the deposition voltage of DU=60V was used.

3.2.1. Density of amorphous aluminium oxide thin lms The density of the aluminium oxide thin lms depended on the target voltage, sputtering gas pressure and substrate bias voltage. The density decreased as a function of the target voltage from a value of 3.57 to 3.00 g cm3 (Fig. 4). The target voltages were between 310 and 360 V. The target voltage for the metallic target was 390 V. The pressure of argon was kept at 1.0 Pa during the deposition. The density of the lms increased as a function of the sputtering gas pressure ( Fig. 4). A pressure of 0.30 Pa yielded an aluminium oxide thin lm with a density of 2.32 g cm3, which increased to 3.00 g cm3 at a pressure of 1.0 Pa. Thin lms with a high density were obtained when the substrate bias voltage was used. At bias voltages of 100 and 150 V, the densities were 3.65 and 3.77 g cm3, respectively. Previous literature reports values of between 2.1 and 3.6 g cm3 for the density of amorphous aluminium oxide thin lms [48].

Fig. 3. Deposition rates of transparent aluminium oxide thin lms.

Fig. 4. Density of amorphous aluminium oxide thin lms related to sputtering gas pressure and deposition voltage.

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3.2.2. Nanohardness of aluminium oxide thin lms The nanohardness of the aluminium oxide thin lms was measured from samples deposited on the 0.55-mmthick Si substrate. The nanohardness was between 12.5 and 13.0 GPa over the target voltage range between 310 and 360 V. The sputtering gas pressure had a strong inuence on the nanohardness of the unbiased samples, however. Low sputtering gas pressures led to a high nanohardness, whereas high pressures led to a low nanohardness (Fig. 5). At a pressure of 0.30 Pa, the nanohardness was 20.6 GPa, decreasing to a value of 12.6 GPa at a pressure of 1.0 Pa. The sputtering gas pressure was held at 1.0 Pa when the bias voltage was a parameter. The nanohardnesses of the thin lms were more than 18 GPa when substrate bias voltages of 40 or 60 V were used (Fig. 5). The nanohardness then decreased towards high substrate bias voltages. The nanohardness was between 13.5 and 16.0 GPa at 150 and 200 V substrate bias voltages. The literature reports values of 712 GPa for the nanohardness of amorphous aluminium oxide thin lms [4,911]. 3.2.3. Intrinsic stress of aluminium oxide thin lms The pressure of the sputtering gas has an important role in intrinsic stress. The thin lms deposited at a low pressure represented compressive stress between 250 and 50 MPa ( Fig. 6). The stress turned from compressive to tensile of 175 MPa when the pressure was increased to 1.0 Pa. Fig. 6 also shows the interdependence of the thin lm density and the residual stress as a function of the sputtering gas pressure. The residual stress of amorphous aluminium oxide thin lms has been reported to have values between 90 and 680 MPa [1215].

Fig. 6. Eect of sputtering gas pressure on residual stress and density of aluminium oxide thin lms.

4. Discussion The voltage-controlled deposition process has excellent long-term stability. The metal and compound modes

Fig. 5. Nanohardness of aluminium oxide thin lms as a function of sputtering gas pressure and substrate bias voltage.

of the aluminium target can be controlled by the target voltage. Because of this, the deposition rate and the O/Al ratio can be chosen by a given target voltage. However, the target power has to be taken into account. The target voltage increased as a function of the target power. The impedance between the electrodes remains the same at a constant target voltage value. The target voltage corresponds to the secondary electron emission coecient determined by the impinging ions and the target coverage. The sputtering yield of the aluminium atoms, the electron and ion emissions are in a constant region. A slight target poisoning was, however, observed. The oxygen gas ow rate has to reduce during the deposition to maintain a constant target power. A high rate of sputter deposition can be obtained with small DU values when the target remains at the metal mode. The density of the aluminium oxide thin lms was dependent on the target voltage, and thus on the O/Al ratio of the thin lms. The coating density can also be aected by sputtering gas pressure and the substrate bias voltage. The high target voltage values led to a small O/Al ratio, which, in turn, led to low-density thin lms (Fig. 4). At a low sputtering gas pressure, the thin lms were less dense than the lms deposited at high pressure. The collision and scattering phenomena between the particles at a low pressure are more intensive, thereby leading to less dense thin lms. The substrate bias voltage densied the aluminium oxide thin lms. The substrates were surrounded by plasma when the bias conditions were used. This plasma leads mainly to energetic oxygen radical formation and enhanced argon ion bombardment. The nanohardness was not dependent on the O/Al ratio. The nanohardness was constant over the O/Al range between 1.30 and 1.72. The chemical composition of the lms was practically the same when the thin lms were transparent insulators. Hardness is a complex property related to the microstructure of the lm and to the strength of interatomic forces, and depends on more than one variable. A smooth thin lm surface with small R values represents a high hardness. Porous lms a

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with microvoids led to small nanohardnesses. Lowpressure lms represented hard thin lms (Fig. 5). The microstructure of the lms could be dense and could therefore include few voids. The low substrate bias voltages resulted in a very high nanohardness, too. The residual stress depended on the coating density and thus microstructure of the thin lm (Fig. 6). The trapped argon atoms in the thin-lm structure could increase the density of the thin lm, and this in turn, could lead to an increased tensile stress. The low-density thin lms had a slight compressive stress. The substrate bias voltage increased the compressive stress in the lm due to the densication eect and the atomic peening mechanism. The relationship between nanohardness and residual stress can be seen from Figs. 5 and 6. Hard thin lms deposited at a low pressure represented thin lms with higher compressive stress levels than thin lms deposited at high pressures. These thin lms represented a low nanohardness and tensile stress. The phenomena related to nanohardness and residual stress are assumed to be due to dierences in the microstructure and nanocrystallization phenomena in an amorphous matrix.

ing gas pressure and low bias voltages led to aluminium oxide thin lms with a high hardness and low intrinsic stress. High sputtering gas pressure, high substrate bias voltage and low target voltage led to dense aluminium oxide thin lms. The thin lms with smooth surface were obtained when low sputtering gas pressure and high bias voltages were used. The O/Al ratio can be controlled by the target voltage.

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5. Conclusions A voltage-controlled reactive magnetron sputtering process has been shown to be useful for aluminium oxide thin lms. The problems of poor deposition rates and unstable processes can be overcome using this technique. Moreover, the reactive gas inlet in the vicinity of the substrates improves the oxidation of the thin lms and decreases the target poisoning. The process parameters aect the thin-lm properties. Low sputter-