Thin Solid Films 515 (2007) 3675 3680 www.elsevier.

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Characterization of nano-composite TiNSb coating produced with hybrid physical vapor deposition system
K. Kazmanli , B. Daryal, M. Urgen
Istanbul Technical University, Department of Metallurgical and Materials Engineering, 34469 Istanbul/Turkey Received 17 January 2006; received in revised form 12 September 2006; accepted 31 October 2006 Available online 15 December 2006

Abstract In the present study, antimony was doped into TiN film by using hybrid physical vapor deposition method. Cathodic arc evaporation and magnetron sputtering was used for co-deposition of Ti and Sb, respectively. The coatings were analyzed by means of X-ray diffraction, Raman spectroscopy and scanning electron microscopy. Crystallite sizes of the coatings were calculated with WilliamsonHall Method by using X-ray diffraction patterns. The results of crystallite size calculations were supported with Field Emission Gun Scanning Electron Microscopy fracture cross section observations and also with micro Raman investigations. TiN and TiNSb coatings were tested against Al2O3 ball by means of ballon-disc method in order to understand the contribution of Sb to tribological properties of TiN coating. Hardness of the coatings was measured using depth sensing indentation technique. The relationship between Sb content of the films and hardness is established. The results indicated that antimony addition into TiN film facilitated the nanosize TiN crystal formation. A small amount of Sb (1.8 at.%) in TiN provided the maximum hardness value of 38 GPa. When crystal size dropped to approximately 5 nm, the nano-composite coatings softened abruptly down to a hardness of 18 GPa. Tribology test results showed that Sb addition to TiN coatings decreased friction coefficient. While TiN coating had friction coefficient between 0.5 and 0.6, TiNSb coating had lower friction coefficient between 0.17 and 0.35. 2006 Elsevier B.V. All rights reserved.
Keywords: Nano-composite coating; TiNSb coating; Hybrid coating system; Friction coefficient

1. Introduction In the last decade, nano-composite coatings have become very popular because of their high toughness and stiffness along with their superior hardness. Superior properties of these coatings make them promising candidates in mechanical and tribological applications [17]. In the literature, nano-composite coatings have been mainly divided into two categories: (a) hard MeN-hard phase, (b) hard MeN-soft phase. Veprek [1,810] proposed a nano-composite coating model based on hard MeN-hard phase type coatings. In this model, boundaries of the hard nanosize grains (MeN grains) were reinforced with a hard and preferably amorphous nanophase. According to Veprek's model, two hard nano-phases with strong grain boundaries in a coating could substantially
Corresponding author. Tel.: +90 212 2853537; fax: +90 212 2853427. E-mail address: kursat@itu.edu.tr (K. Kazmanli). 0040-6090/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2006.10.138

increase the hardness above 50 GPa. On the other hand, Musil [2,1113] developed another approach for nano-composite coatings that is based on the existence of a hard (MeN type) and soft nano-phases (X, metallic). The relatively softer phase (X) acts as an obstacle against dislocation movements at grain boundaries because of elastic modulus difference between grains and grain boundary phases. Elastic modulus difference is expected to increase the hardness of the coatings with the same mechanism as in the super-lattice ones [2,11]. However, in cases where grain sizes are less than approximately 10 nm, the increasing amount of grain boundaries, will dominate the plastic deformation by grain boundary sliding. Hence, hardness of the coatings will decrease. In order to form nanocrystalline/amorphous composite, components of the coatings should show a strong thermodynamically driven segregation [10]. There are a number of studies that aims to produce nc-MeN/a-Si3N4, nc-MeN/a-BN and ncMeN/CN (Me = Ti, Hf, V, Nb, Ta, Cr and other transition metals)

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nano-composite structures by using this approach, [46,8 10,1419]. On the other hand, mutually immiscible metallic elements in nitride coatings can also form a relatively soft phase at grain boundaries [2]. Generally, Cu [7,11,20], Ag [2123], Ni [12,24,25], Y [26] and Co [27] were doped into TiN, CrN, ZrN and MoN coatings as the soft phase to form MeNX type nanocomposite structures. Crystal system incoherency of components in a multicomponent film should also be considered as another determinant factor on the structural morphology of a growing film [28]. In the case of a lattice mismatch or big difference in lattice constants of the film constituents, the component with the lower concentration in the system cannot incorporate into the matrix crystal and will form its own nuclei and crystals, separately. It is well known that these secondary nuclei will obstruct the matrix phase growth. Amorphous phase formation is also possible in such a system in consequence of big lattice mismatch [28]. Considering these nano-composite formation conditions, it is possible to design nano -composite coatings which can serve in specific application areas. Because antimony has been used commonly in bearing alloys because of its low friction coefficient providing oxides [29,30], antimony containing nano-composite coatings may possibly find an application in tribology. Hence, antimony is immiscible in Ti and has rhombohedral crystal system, it can be used for the nano-composite formation in cubic TiN. The immiscibility in Ti and the expected lattice mismatch arousing from different crystal systems increases the nano-composite formation possibility of Sb in TiN films. However, antimony has not been studied in nano-composite concept so far. From the nano-composite film formation standpoint, addition of antimony into commonly used cubic TiN film deserves to be investigated. The coating technique used in this study is a hybrid physical vapor deposition method which consists of cathodic arc and magnetron sputtering evaporation techniques. Cathodic Arc Magnetron Sputtering Hybrid System has also been used previously to form nano-composite coatings [7,1820,31]. Cathodic Arc Physical Vapor Deposition (CAPVD) is a well known technique with its high ionization capability, high deposition rate, and ability to produce very well adherent coatings. However, it has a major drawback of macro particle production which becomes very pronounced during evaporation of low melting point elements. In this study, low melting point component, namely Sb, of the coating is introduced into titanium plasma created by CAPVD, through sputtering. In this manner, it is aimed to join the advantages (dense, well adherent CAPVD, smooth, macro particle free-magnetron sputtering) of both coating techniques in the production of TiNSb nanocomposite structures. 2. Experimental studies 2.1. Preparation of the coatings Hardened high speed steel substrates were polished to the surface roughness of Ra = 0.08 m and ultrasonically cleaned in a

hot alkaline solution. Right after the cleaning, the samples were placed in a vacuum chamber in order to prevent from contamination of the surfaces. A hybrid coating system consisting of one cathodic arc and two magnetron sputtering sources were used. Nitrogen was used as process gas for sputtering of Sb targets and kept constant at 1 Pa for all coatings. In order to obtain desired Sb content within the coatings, the sputtering power of Sb target and arc current of Ti cathodes were changed in the range of 100 300 W and 5075 A, respectively. The number of Ti cathodes was also changed to adjust the composition of the coatings. Before the coating process, substrates were ion-cleaned and heated by Ti ion bombardment for 3 min. The ions were accelerated toward the substrates with 1 kV bias voltage. After ion cleaning, all samples were coated without bias voltage for 1 h. 2.2. X-ray diffraction, Raman spectroscopy and scanning electron microscopy studies Phase structure of the coatings was identified by a glancing angle X-ray diffractometer with a thin film attachment (using Cu-K radiation) and by Raman Spectroscopy. The scan method with a fixed incidence angle of 1 was used for X-ray Diffraction (XRD) studies. For Raman studies, a HeNe laser having 632.8 nm wavelength and 0.86 m spot size was employed. Approximate crystallite size of the coatings was calculated by means of WilliamsonHall Integral Breadth Method using XRD patterns. Detailed description of the theory can be found in the literature [32,33]. Sb content of the coatings was measured by means of energy dispersive spectroscopy (EDS) attached to a Scanning Electron Microscope (SEM). Twenty (20) kV acceleration voltage was used for EDS analysis. Data collection time for every EDS analysis was 3 min. Cross-sectional morphology observation of the coatings was carried out by Field Emission Gun SEM. The cross-section surfaces were prepared by breaking the samples in liquid nitrogen. 2.3. Hardness measurements Hardness and elastic modulus of the coatings were measured by means of depth sensing ultra micro hardness indentation (using Vickers indenter) method. In order to prevent the hardness measurements from substrate effect, maximum 15 mN load was applied to the coatings surface. The Vickers indenter was penetrated in 120 steps and time interval between the steps was 0.5 s. After reaching the final load, the indenter was retracted with the same parameters as in the loading cycle. Hardness and elastic modulus of the coatings were measured from the collected data by using loading and unloading loadpenetration depth curve. Detailed explanation of the calculation procedures for hardness and elastic modulus can be found in the literature [9,3436]. 2.4. Tribology tests In order to investigate the effect of antimony on the tribological property of TiN coatings, ball-on-disc tests were

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conducted on TiN and TiNSb coatings. The sample was tested against Al2O3 balls with 10 mm diameter at room temperature. Normal load, sliding distance, linear sliding speed and relative humidity were 2 N, 50 m, 2 cm/s and 50%, respectively. 3. Results and discussion 3.1. X-ray diffraction studies and crystallite size calculations Antimony contents of the samples were analyzed by using EDS and given in Table 1. One of the samples (sample 1) was coated using only Ti cathode so as to form pure TiN film. The other samples were doped with different amounts of Sb (minimum 0.8 at.% Sb: sample 2 and maximum 12.6 at.% Sb: sample 6). The results showed that it is possible to dope Sb into TiN and adjust Sb content of the coatings by the hybrid deposition technique utilized in this study. The XRD patterns (Fig. 1) revealed formation of cubic-TiN for all samples. When 5.5 at.% Sb was added into TiN matrix, a broad hump around (012) Sb diffraction peak started to show up. This is an indication of the formation of an amorphous or nanocrystalline Sb phase in TiN matrix (Fig. 2a). Intensity of the hump became higher with increasing Sb content. Furthermore, TiN matrix peaks broadened and shifted towards lower diffraction angles with increasing antimony amount (Fig. 2b). The broadening of TiN peaks started to be distinctive after 1.8 at.% Sb. The grain sizes and lattice strains of TiN crystals were calculated according to the procedure given in Section 2.3. The calculation results were listed in Table 1. In consequence of Sb incorporation into the coatings, the matrix phase became clearly nanosized after the introduction of 1.8 at.%. Sb into the coatings. Grain size of un-doped TiN sample was approximately 186 nm. Only 5.5 at.% Sb addition reduced the grain size of TiN crystals drastically down to 5 nm scale (Fig. 3a). Moreover, the calculations pointed out a decrease in lattice strain of TiN crystals as well (Fig. 3b). Clearly, the reduction of crystallite size down to a few lattice constant inhibited the formation of lattice planes with different lattice parameters within the same crystal so as to diminish the lattice strains. 3.2. Raman studies Raman spectrum of sample 1 (Fig. 4a) is similar to the spectrum reported for TiN in the literature [31,37]. In our study, Raman peaks were observed at 210, 310, 419 and 556 cm 1 for
Table 1 Analysis and grain size calculation results of TiN and Sb-doped TiN samples Sample no 1 2 3 4 5 6 Sb contents at.% 0.0 0.8 1.8 5.5 9.8 12.6 Thickness m 2.0 2.0 1.5 1.2 1.8 1.2 Grain size Dv, nm 186 178 86 5 6 6 Strain 0.00188 0.00157 0.00170 0.00113 0.00125 0.00135 Hardness GPa 31 36 38 18 8 7.7 Elastic modulus GPa 323 378 378 210 144 133

Fig. 1. X-ray diffraction spectra of TiN and Sb-doped TiN coatings.

sample 1. Cheng et al. [37] reported the same peaks with a slight shift to higher wave numbers for TiN in their work for CAPVD TiN coatings. When antimony was doped into TiN film, a broad peak started to show up at 153 cm 1 (Fig. 4b). This peak was the Raman shift induced by Sb as previously reported [38,39]. By increasing the Sb content of the film, this peak became more intense and distinctive while, on the other hand, TiN peaks started to loose their intensity (Fig. 4c, d). The Sb incorporation into TiN matrix was not noticeable for 1.8 at.% Sb in XRD pattern because the Sb phase was amorphous or had very smallnanosized crystals. However, Raman spectrums revealed the Sb phase formation which could not be observed in XRD patterns. Frequency, width, and intensity of Raman peaks depend on lattice defects, composition, crystal size, structure, and internal stress of materials [31,37,40]. In consequence of reflection of the phonon at grain boundaries, the phonon can be confined within the isolated nanosize grains. Arora et al. [40] reported that phonon confinement effect was noticeable on the Raman spectra only when the grain size is smaller than 20 lattice parameters. However, this type of phonon propagation cannot be observed, in larger grains. Similarly, Zhu et al. [41] found a relation between the size of TiO2 particles and their Raman spectra that the Raman peaks asymmetrically broadened as the particles became nanosized. In our study, TiN Raman peaks were broadened and lost their intensity when their crystallite size became 5 nm as shown in Fig. 4 (for 5.5 at.% and more Sb). The nanosized crystals of the coatings can be the reason for the low intensity and the line broadening of the TiN Raman peaks. 3.3. Cross sectional scanning electron microscope observations The cross sectional SEM observations of TiN coating exhibited a columnar morphology (Fig. 5a). Antimony inclusion with amount of 1.8 at.% into the TiN film diminished the

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columnar morphology to some extent (Fig. 5b). 5.5 at.% Sb in TiN coating changed the morphology of the coating from the columnar (Fig. 5a) to the featureless one (Fig. 5c). Further Sb additions into the coating above this critical Sb content led the TiN crystals to be nanosized. The SEM micrographs, crystallite size calculations, XRD and Raman studies pointed out the same critical antimony content that TiN crystals started to be nanosized after 5.5 at.% Sb addition. The mutual immiscibility of coating's components is one of the nano-composite coating formation factors [2]. On the other hand, the lattice mismatch between matrix and dopant component is also important from the crystal system point of view. A considerable difference in crystal systems or lattice parameters of a growing film drives the crystal formation towards an amorphous structure [28]. The crystal systems of TiN phase (cubic) and Sb (rhombohedral) might have an important role on the nano-composite film formation. Due to this crystal system mismatch and mutual immiscibility of the metallic components, Sb is not incorporated in TiN matrix but

Fig. 3. Relationship between Sb contents and (a) hardnessgrain size, (b) lattice strain of the coatings.

forms separate nuclei during film growth. Therefore, the growth of TiN crystals was stopped by the Sb nucleus so as to form the nanosize TiN grains. 3.4. Hardness measurements Hardness and elastic modulus of the coatings were measured by using loading and unloading indentation data collected from the depth sensing hardness tester. A sample loading and unloading indentation curve was given in Fig. 6. The hardness measurements showed that antimony increased the hardness of TiN coating from 31 GPa to 38 GPa with the addition of only 1.8 at.% Sb (Table 1 and Fig. 3). The crystallite size of this coating (sample 3) was 86 nm. The presence of Sb in the film reduced the grain size, and thus, dislocation distance in TiN crystals. This hinders the dislocation movements at the grain boundaries where lower elastic modulus Sb phase formed. More

Fig. 2. X-ray diffraction patterns of the coatings: (a) (012), (003) and (101) Sb crystal plane, (b) (111) TiN crystal plane.

Fig. 4. Raman spectra of the coatings: (a) TiN, (b) 1.8 at.% Sb, (c) 5.5 at.% Sb, (d) 9.8 at.% Sb.

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Fig. 6. Loading and unloading indentation curve of 1.8 at.% Sb containing TiN Sb coating.

3.5. Tribological experiments Friction coefficient of TiNSb sample was lower than that of TiN coating (Fig. 7). TiN samples gave very high friction coefficients (approximately 0.8) at the beginning of the experiments which then dropped to 0.5. Throughout the test, friction coefficient gradually rose to 0.6. On the other hand, Sb addition to TiN matrix lowered friction coefficient to approximately 0.17. Friction coefficient of TiNSb coating gradually increased to 0.35 during the test. The tests revealed that Sb has an obvious lowering effect on the friction coefficient to TiNSb coatings. In the literature, the beneficial effect of antimony on tribological properties is attributed to the lubricious character of its oxides which are formed during sliding [29,30]. These preliminary results showed that further investigations on the beneficial role of the antimony introduction into hard coatings for tribological applications are required.

Fig. 5. Cross section micrographs of TiN coatings with (a) TiN, (b) 1.8 at.% Sb, (c) 5.5 at.% Sb.

Sb addition (5.5 at.%) caused the hardness of the coating to drop steeply to 18 GPa with the formation of nanosize TiN crystals (5 nm). The soft Sb phase surrounding the nanosize TiN grains dominated the deformation by the grain boundary sliding. Therefore, more Sb incorporation into the film drastically decreased the hardness of the coatings to a minimum value of 7.7 GPa for the highest Sb amount (12.6 at.%). Also, the elastic modulus of the coatings decreased with increasing amount of Sb in the film (Table 1). Maximum and minimum hardness values were 38 GPa for 1.8 at.% Sb and 7.7 GPa for 12.6 at.% Sb.

Fig. 7. Friction coefficientssliding distance curve of TiN and 1.8% Sb doped TiNSb coatings.

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4. Conclusions In the present study, TiNSb nano-composite coatings were produced using a hybrid system consisting of cathodic arc and magnetron sputtering sources. The magnetron sputtering source in the hybrid system facilitated the incorporation of the low melting point Sb into the high energetic arc plasma of Ti. This hybrid system configuration also gave flexibility for adjustment of dopant contents within the composite coatings. Antimony in TiN coatings showed very broad and low intensity diffraction peaks and had an amorphous or nano-composite structure. Raman spectroscopy method was used to identify the amorphous Sb phase which did not give any diffraction peaks but a broad hump in the XRD patterns. The results indicated the complementary role of Raman spectroscopy for the identification of the composites consisting of amorphous and crystalline components. The cross sectional SEM micrographs of the coating with 5.5 at.% Sb addition showed a featureless morphology. The critical antimony content for the nanosize crystal formation (below 10 nm) and for the structural morphology change from columnar to featureless, was determined as 5.5 at.%. After nanosize crystal formation, the hardness of the coatings dropped to a minimum of 7.7 GPa. for 12.6 at.% Sb containing coating. TiN coating (produced by using CAPVD method) had 186 nm crystal size and 31 GPa hardness. Incorporation of antimony into TiN decreased the crystal size of TiN matrix. A small amount of Sb (1.8 at.%) in TiN caused the crystal size to decrease to 86 nm and provided maximum hardness of 38 Gpa. Further antimony addition (5.5 at.% Sb and more) into the coating made the matrix crystal become nanosized (approximately 5 nm) and this nanocrystal formation decreased the hardness of the coatings to 18 Gpa. The critical antimony contents were determined as 1.8at.% for the highest hardness and 5.5 at.% for the formation of nanosize grains (below 10 nm). Preliminary tribology test results showed that Sb addition provided lower friction coefficients. While TiN coating against Al2O3 ball gave a friction coefficient between 0.5 and 0.6, the friction coefficient of Sb doped TiN (1.8 at.% Sb) coating was between 0.17 and 0.35. Acknowledgements The present work was a part of the Advanced Technologies in Engineering and Production and Development of Low Wear and Low Friction Coefficient Providing Nano-composite Coatings for High Temperature and Power Systems projects supported by State Planning Organization of Turkey. Ahmet Ozturk's and Berk Demirel's technical assistance during preparation of the coatings and Dr. Gultekin Goller's and Huseyin Sezer's kind support for FEG-SEM investigations are gratefully acknowledged. References
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