WC/a-C nanocomposite thin films: Optical and electrical properties

M. D. Abad, J. C. Snchez-Lpez, N. Cusnir, and R. Sanjines Citation: J. Appl. Phys. 105, 033510 (2009); doi: 10.1063/1.3060717 View online: http://dx.doi.org/10.1063/1.3060717 View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v105/i3 Published by the AIP Publishing LLC.

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JOURNAL OF APPLIED PHYSICS 105, 033510 2009

WC/a-C nanocomposite thin lms: Optical and electrical properties

M. D. Abad,1 J. C. Snchez-Lpez,1 N. Cusnir,2 and R. Sanjines2,a
1 2

Instituto de Ciencia de Materiales de Sevilla, CSIC-US, Sevilla 41092, Spain Ecole Polytechnique Fdrale de Lausanne, IPMC-SB, CH-1015 Lausanne, Switzerland

Received 28 August 2008; accepted 21 November 2008; published online 5 February 2009 WC/amorphous carbon a-C thin lms were deposited by dual magnetron sputtering from individual WC and graphite targets. The inuence of lm composition and microstructure on the optical and electrical properties was investigated. As evidenced by x-ray photoelectron spectroscopy and grazing angle x-ray diffraction measurements, the WC/a-C lms are composite materials made of hexagonal W2C and/or cubic -WC1X nanocrystallites embedded in a-C matrix. The optical properties were studied by spectroscopic ellipsometry and the electrical resistivity was measured by the van der Pauw method between 20 and 300 K. Both the optical and the electrical properties of the WC/a-C lms are correlated with the chemical composition and microstructure evolution caused by a-C addition. The optical properties of W2C / a-C and -WC1x / a-C lms with a-C content 10 at. % are explained by modeling their dielectric functions by a set of DrudeLorentz oscillators. Further increase in a-C content leads only to the formation of -WC1x / a-C nanocomposite structures and their optical properties progressively evolve to those of a-C single phase. The electrical resistivity as a function of the temperature of all the lms exhibits a negative temperature coefcient of resistivity. Theoretical tting using the grain-boundary scattering model shows that the transport properties are mainly limited by the grain size and electron mean free path parameters. 2009 American Institute of Physics. DOI: 10.1063/1.3060717
I. INTRODUCTION

In the past years, nanocomposite coatings made of transition-metal carbides dispersed in amorphous carbon a-C matrix, such as the WC/a-C system, have been widely studied especially for their physical and mechanical properties.1 They exhibit high melting point, extreme hardness, low coefcient of friction, chemical inertness, oxidation resistance, and good electrical conductivity. These properties make them ideal candidates for various industrial applications such as wear-resistant coatings, cutting, and drilling tools. The high hardness may be explained by their nanocomposite structure of the lms.2 Nanocomposite coatings are composed of nanocrystalline materials with a grain size of approximately 10 nm or less surrounded by a second nanocrystalline or amorphous phase grain boundary region.3 This kind of structure also allows a high thermal stability of the coatings.4 In addition, the unusual combination of strong bonding and metallic conductivity makes tungsten carbide an attractive material for high temperature electrical contacts or as conductive protective layers in sensor applications. Binary tungsten carbide usually crystallizes in a hexagonal phase as W2C or WC while substoichiometric WC1x can crystallize in a cubic phase. In composite materials such as WC/a-C two or three phases can be present and the resulting lm structure can be rather complex due to their chemical heterogeneity and phase distribution at the nanoscale. In this sense, the measurement of optical or electrical properties can shed light on the relationship between the crystalline phases, microstructure, and the fundamental properties of these
a

lms. The optical and electrical properties of protective coatings have been generally measured on transition-metal nitride thin lms: TiN,5 ZrN,6 ZrSiN,7 ZrAlN,8 NbSiN,9,10 and TiBN.11,12 Less information is found for the transition metal carbide series: WC,1316 ZrC,17 TiC,17,18 TiSiC,19 and TiBC.20 A fewer publications are devoted to their combinations with a-C as nanocomposite structure. Park et al.21 studied the electrical resistivity of WCC nanocomposites, and De Temmerman et al.22 studied the inuence of the optical properties for MoxC1x. The present paper reports an extensive analysis of the optical and electrical properties of the WC/a-C coatings. This nanostructured system material has been rather investigated previously, either in the form of nanocomposite or multilayer, for the improvement of the tribological performance and hardness.2328 The present study is of interest both for fundamental reasons and for technological applications. Stoichiometric deviations, structural disorder, and phase composition inuence the physical properties of these materials. Moreover, knowledge on the relations between the microstructure and electrical and optical responses of disordered two-phase nanocomposites leads to a better understanding of their functional properties.
II. EXPERIMENTAL

Electronic mail: rosendo.sanjines@ep.ch.

The WC/a-C coatings were prepared by dual magnetron sputtering from two individual WC Kurt J. Lesker, 99.5% purity and graphite Goodfellow, 99.5% purity targets. A dc magnetron source was used in the case of graphite target and a rf source for the WC target. The residual pressure in the reactor was 3 104 Pa and the total pressure during the deposition was kept constant at 0.6 Pa. A series of WC/a-C
2009 American Institute of Physics

0021-8979/2009/1053/033510/6/$25.00

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FIG. 1. Diffractograms for the WC/a-C lms as a function of the SPR.

coatings has been prepared by changing the sputtering power ratio SPR, dened as SPR= PC / PWC, from 0 to 3. The typical power PWC values applied to the WC target were 150 and 250 W, while those applied to the graphite target were varied from 0 to 450 W. The obtained lms are labeled as R0, R0.1, R0.3, R0.5, R1, R2, and R3. The substrates were mounted on a rotary sample holder 10 rpm to ensure homogeneity and the temperature was found to vary in the range of 150 200 C under the effect of the plasma. In the case of R0 lm the substrate was dc polarized at 100 V. No additional heating of the substrates was performed. Typical lm growth times were about 4 h and lm thicknesses range from 0.75 to 2.0 m as measured by means of stylus prolometry. The substrates used were silicon, M2 steel, and silicon oxide for the electrical properties. The crystal structure of the lms was examined by grazing angle x-ray diffraction XRD analysis using Cu K radiation 0.154 nm in a Siemens D5000 diffractometer at an incidence angle of 1 in order to increase the signal from the coating compared with the substrate. The x-ray photoelectron spectroscopy XPS equipment is a VG-Escalab 210 spectrometer working in the constant analyzer energy mode with pass energy of 50 eV and nonmonochromatic Mg K radiation 1253.6 eV as excitation source. Samples were previously cleaned using Ar+ ion bombardment 2.5 103 Pa; 2.5 kV; 300 s. For quantication, the XPS spectra were subjected to background subtraction Shirley background and sensitivity factors supplied by the instrument manufacturer were used. The ellipsometric measurements were performed in the photon energy range of 1.55.0 eV using an Uvisel Jobin-Yvon ellipsometer at an angle of 70. A simple semi-innite model was used to calculate the dielectric function of the lms. Electrical resistivity was measured by the van der Pauw method in a temperature range between 20 and 300 K.
III. RESULTS AND DISCUSSIONS A. Structure and chemical composition

Figure 1 shows the change in the XRD patterns of the WC/a-C lms with the applied SPR. The comparison of the diffractrograms with the XRD database29 permits the identication of the phases. The R0 lm, grown by sputtering from

the single WC target, crystallizes in the hexagonal W2C phase with a marked 002/101 orientation. There are two hexagonal forms of W2C phase and that differ mainly in the arrangement of the carbon atoms. The small differences in lattice constants are only visible at low 2 angles.30 Due to their similar interplanar distances we use hereafter the general form W2C phase without specifying the crystallographic structure. From the broadening of 100 and 002/ 111 reection peaks an average crystallize size of 9 nm was estimated using the Scherrer formula. As the SPR is slightly increased to 0.1, the XRD pattern of R0.1 lm exhibits an additional small peak located at about 2 = 42 while the intensity of the 002/111 is strongly reduced. The new peak is attributed to the 200 reection peak of the cubic -WC1x phase. These results suggest that the R0.1 lm is a double phase lm containing W2C and -WC1x phases. The crystallite size in W2C was reduced to about 7 nm, while in -WC1x the crystallite size is estimated to be about 5 nm. In contrast, for higher SPR values, the diffraction patterns of the associated lms exhibit mainly a broad peak located at about 2 = 38, which can be associated with the 111 reection peak of the fcc -WC1x phase; a rough estimation gives a crystallite size of 23 nm. Thus, the incorporation of carbon into the W2C lms by increasing the SPR parameter leads to a progressive reduction in the crystalline domain size, the nucleation of the cubic -WC1x phase and, at higher C content, the formation of composite lms containing nanocrystallites of cubic -WC1x phase dispersed in an a-C matrix. It is important to note that neither peaks from hexagonal WC nor from crystalline graphite have been detected despite of the sputtered target was WC, as it was reported elsewhere.31,32 The chemical composition of the coatings was determined by XPS analysis after cleaning the surface of samples by ion bombardment. The elemental atomic percentages deduced from the W 4 f , C 1s, and O 1s photoelectron peaks are summarized in Table I for the different synthesis conditions. Although ion bombardment can introduce spurious effects in the determination of the chemical composition absolute values due to selective sputtering and chemical bonding modications, the obtained relative values are representative of the investigated samples. Figure 2 shows the variation in the W, C, and O atomic percentages as a function of the synthesis conditions. The average oxygen contamination remains low, typically in the range of 3 5 at. %. The total carbon content in the lms progressively increases from 32.3 to 75.3 at. % as the SPR is changed from 0 to 3. In order to obtain more quantitative insights of the compositional changes, the W 4 f and C 1s peaks were tted to evaluate the contributions of WC and amorphous CC bonds. The obtained values are also summarized in Table I. From R0.3, the content of free carbon increases continuously with increasing the SPR values, while the carbide components tend to reach a steady-state value. According to these results, the C/W ratio is found to vary in a range from 0.4 to 1.3, indicating the formation of nonstoichiometric WC phases. These results are not surprising since transition metal nitrides5,6 and carbides33,34 are rather nonstoichiometric materials and have tendency to incorporate appreciable vacancy concentrations

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TABLE I. Total elemental chemical composition at. % and distribution in WC and a-C phases for the WC/a-C lms. W at. % 63.5 58.2 47.6 39.6 32.1 27.6 19.9 0 C at. % 32.6 37.3 49.4 55.1 64.4 69.2 75.3 100 O at. % 3.8 4.4 3.0 5.3 3.5 3.2 4.7 0 WWC % 66.4 61.8 50.3 43.9 34.7 30.3 23.9 0 CCW % 26.6 35.3 39.6 40.1 39.5 39.4 31.0 0 Ca-C % 7.0 2.9 10.1 16.0 25.8 30.3 45.1 100

Film R0 R0.1 R0.3 R0.5 R1 R2 R3 a-C

SPR 0 0.1 0.3 0.5 1 2 3

on both the metal and nonmetal sublattices. In substoichiometric carbides the most signicant defect is the C vacancy while in C-rich compounds excess C behaves like an interstitial defect, forming a metastable solid solution,25,32 although the presence of W vacancies cannot be ruled out completely.

According to the band structure calculations reported by Hugosson et al.33 hexagonal W2C and cubic -WC1x phases are metallic compounds with free metal d bands at the Fermi level. In good agreement with these results, samples from R0 to R0.3 show a Drude-like metallic behavior. In metallic compounds the plasma frequency p is related to the effective density of free electrons N by the relation

B. Optical properties

p =

All the investigated lms are optically opaque; therefore they can be considered as semi-innite samples for ellipsometry and the measurements provide directly the complex dielectric function of the bulk lm without any contribution from the substrate. Figure 3 shows the real and imaginary parts of the dielectric function = 1 + i2 of the composite WC/a-C lms. The spectrum obtained for an a-C lm prepared by sputtering is included as a reference. The optical properties of the a-C lm are comparable to those observed in previous works for semimetallic a-C samples.35,36 The pseudodielectric functions of R0 W2C and R0.3 -WC1x lms as well as that of the R0.1 lm show a typical Drude-like metallic behavior with 1 0 over the investigated energy range. The 1 curve of the R0 lm exhibits clearly two resonance peaks located at 2.6 and 3.5 eV. These features are also visible in the spectrum of the double phase R0.1 lm containing a mixture of W2C and -WC1x phases. Regarding the W2C phase, it is worth noting that similar curves have been reported for isoelectronic hexagonal Cr2N and Nb2N lms.10,37

e 2N , 0m

where m and e are the effective mass and charge of the electron. The plasma energy p typically lies in the ultraviolet region; however, in transition metal nitrides and carbides interband transitions occurring at energies lower than the plasma energy strongly modify the plasma reectance edge. Following the standard analysis procedure described in Refs. 5 and 10, it is possible to t the dielectric function using a Drude term intraband transitions and a set of Lorentz oscillators interband transitions, =

2 f k 2 p k + , 2 2 + i p k=1 2 + i k k

where is a constant accounting for the all higher-energy interband transitions, p = / is the damping factor, and is the free electron relaxation time. Four Lorentz oscillators have been introduced to account for interband transitions. Under the assumption that R0 and R0.3 lms are single

FIG. 2. Color online Total atomic percentages of W, C, and O estimated by XPS vs the SPR.

FIG. 3. Color online a Real 1 and b imaginary 2 parts of the dielectric function of WC/a-C lms.

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FIG. 4. Color online Refraction n and extinction k coefcients as a function of the carbon at. % in the WC/a-C lms.

phase materials W2C and -WC1x phases, respectively the 1 and 2 curves of these lms were tted to nd out p and p. Thus p = 7.45 eV and p = 1.5 eV were obtained for the hexagonal W2C lm and p = 6.8 eV and p = 1.5 eV for the cubic -WC1x. For both carbides the electron relaxation time is found to be = 4.3 1016 s while the optical carrier densities were estimated to be NW2C = 4 1022 cm3 for the W2C lm and NWC1x = 3.36 1022 cm3 for the -WC1x lm. The short relaxation time obtained from the tted Drude dumping factor is well correlated with the nanocrystalline and poor crystallized nature of the R0 and R0.3 lms. As deduced from XPS measurements these lms contain about 10 at. % of a-C: the C atoms are principally distributed at the grain boundaries. Therefore, the lattice defects and grain boundary regions limit the mean free path of free carriers to a few nanometers. The optical dc resistivity, which can be extracted from the optical properties as op = m / e2N can be estimated for W2C and -WC1x. The calculated values are op 200 cm for the W2C lm and op 240 cm for the -WC1x lm. These values are consistent with the room temperature dc resistivity values of dc = 140 cm and dc = 180 cm obtained from van der Pauw measurements. Although it is difcult to extract the exact Drude parameter from the optical response of transition metal carbides due to interband transitions, the obtained values conrm the validity of optical method. Finally, the dielectric function of the R0.1 lm lies between those of the R0 and R0.3 lms, which is in good agreement with the presence of W2C and -WC1x phases in this lm as discussed above. In the case of the composite R0.5, R1, R2, and R3 lms, which contain a mixture of two phases, the cubic -WC1x and a-C, the dielectric function gradually evolves toward that of a-C reference lm as the relative concentration of a-C increases. Values for the refractive index n and extinction coefcient k at a xed wavelength of 600 nm are reported in Fig. 4 as a function of the carbon content for all the investigated lms. Both n and k progressively decrease as the carbon content increases in the lms. This decrease is due to the change in the a-C content in the lms and consequently diminishes their metallic character. Similar behavior has been observed in various nanocomposite lms containing metallic carbides in an a-C matrix.22

FIG. 5. WC/a-C and a-C lines are

Color online a Room temperature electrical resistivity of thin lms vs carbon at. % and literature values of WC Ref. 15 Ref. 38. b Electrical resistivity vs temperature T. The solid the best t with the grain-boundary model.

C. Electrical properties

The room temperature dc resistivity for a selected series of composite WC/a-C lms is shown in Fig. 5a as a function of the carbon content. For comparison the resistivity of bulk hexagonal WC Ref. 15 and that of the a-C Ref. 38 are also plotted. The resistivity of the R0 lm W2C is about 140 cm, in good agreement with Krzanowski and Endrino16 who reported an electrical resistivity of 150 cm for a W2C-rich coating. The temperature dependence of the resistivity curves is shown in Fig. 5b. The T curves exhibit a negative temperature coefcient of resistivity characteristic of low degree crystallized materials where scattering of electrons against grain boundaries and point defects become important. According to the grain boundary scattering model,39,40 the electrical resistivity in such materials can be described by

g =

m e vF Ne2

1 L/D K L/D G = G , L L

where m e is the effective mass of the charger carriers, F is the Fermi velocity, N is the density of the charge carriers, D is the grain-size parameter, L is the inner-crystalline mean free path, and G is the mean probability for electrons to pass a single grain boundary.22 In this model, an effective mean free path LG = L GL/D was introduced to describe the electron scattering including the grain size effect. The innercrystalline mean free path L, describing the volume scattering of electrons, is limited by a temperature-invariant elastic scattering at lattice defects and acoustic phonons, namely, le, and by the temperature-dependent inelastic scattering lin, 1 such that L1 = l1 e + lin . The inelastic mean free path is approximated by lin Tp, where and p are materialspecic constants.7,10 The best ts using the model described above are shown in Fig. 5b as continuous lines for every WC/a-C lm. For the theoretical modeling we assumed K 2 6 cm2 using average values of = m e F / Ne 11 10 22 3 N 3.5 10 cm and F 1.0 108 cm s1. For all the investigated lms, the representative values of the tting parameters are listed in Table II.

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TABLE II. Typical parameters obtained for the best t of the electrical resistivity of WC/a-C lms with the grain boundary scattering model. C at. % 32.6 37.3 55.1 69.2

Film R0 R0.1 R0.5 R2

cm
137 108 193 232

Thickness m 0.4 1.5 1.6 1.9

104 nm
0.4 0.2 0.2 0.3

P 0.8 0.8 0.8 0.8

G 0.1 0.2 0.21 0.21

D nm 6 4.5 2.5 2.2

Ie nm 4.2 3 2.2 2.1

Figure 6 summarizes the principal parameters obtained for the t: the elastic scattering free path le, the grain size D, and the transmission probability G. From these results the following conclusions can be drawn out. First, the computed values of grain size, ranging from 6 to 2.2 nm, are in agreement with the estimated values from the broadening of the XRD peaks. Second, in the case of R0 and R0.1 lms the le values grain size D values suggest that the mean free path of electrons is determined mainly by the lattice defects C vacancies and by the grain boundary regions. Third, in the case of -WC1x / a-C nanocomposite lms the transport properties are closely determined by further reduction in the mean free path of electrons and crystallite sizes with le D. In such nanocomposite lms the scattering sites are grain boundary regions and interstitials C or W vacancies. However, it is worth noting that in our -WC1x / a-C nanocomposite lms the presence of grain boundary regions composed of a-C seems to not play a considerable role in the electron scattering mechanisms, as it is observed in the case of transition metal nitride composite lms where insulating Si3N4 or BN as the minority phases strongly affect the electrical resistivity of these compounds.7,12 The observed values of G = 0.1 0.2 indicate that the a-C behaves as semimetallic compound in the grain boundary regions.
IV. SUMMARY AND CONCLUSIONS

The optical properties of WC/a-C lms have been investigated by ellipsometric measurements in the optical range of 1.55 eV. The dielectric functions of W2C and -WC1x phases were described by the standard DrudeLorentz model. The free electron relaxation times and the optical free electron density obtained from the tted DrudeLorentz model are in the ranges of 4 1016 s and N 3 4 1022 cm3. Spectroscopic ellipsometry shows the high sensitivity of optical constants to the chemical composition of the composite WC/a-C lms and it can be used in the composition determination of multiple phase composite lms. The electrical properties of the WC/a-C nanocomposite lms are well correlated with crystal phase formation and morphological evolution as a function of a-C content in the lms. The results of theoretical tting using the grainboundary scattering model allowed the identication of electron scattering mechanisms; point defects in the crystallite bulk constitute the main scattering sites in hexagonal W2C and cubic -WC1x with low a-C content, while in -WC1x / a-C nanocomposites the electron mean free path is limited by the crystallite size. In both type of samples, the grain boundary regions composed of a-C do not play a signicant role. Consequently, electrical and optical measures constitute useful techniques to obtain a complete and consistent description of the evolution of the WC/a-C with increasing a-C content.
ACKNOWLEDGMENTS

Nanocomposite lms made of nanocrystallites of hexagonal W2C and/or cubic -WC1x embedded in an a-C matrix have been deposited by dual magnetron sputtering from WC and graphite targets. The formation of tungsten carbide phases was evidenced by XRD measurements and the chemical composition was determined by XPS analysis.

The authors are grateful to the Spanish Ministry of Science and Innovation Project Nos. MAT2004-01052 and MAT2007-66881-C02-01 and to the Swiss National Science Foundation for nancial support.
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FIG. 6. Color online Elastic scattering free path le, grain size D, and transmission probability G as a function of the carbon atomic concentration.

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