Adhesion improvement of plasma-deposited silica thin lms on stainless steel substrate studied by x-ray photoemission spectroscopy and in situ

infrared ellipsometry
villona) N. Bertrand and B. Dre
Laboratoire de Physique des Interfaces et des Couches Minces (UPR 258 CNRS), Ecole Polytechnique, dex, France 91128 Palaiseau Ce

ne maud A. Gheorghiu and C. Se

Laboratoire de Chimie-Physique (URA 176 CNRS), 11 rue Pierre et Marie Curie, 75005 Paris, France

L. Martinu and J. E. Klemberg-Sapieha

Engineering Physics Department, Ecole Polytechnique, P.O. Box 6079, Station Centre-ville, Montreal, bec H3C 3A7, Canada Que

Received 2 April 1997; accepted 10 October 1997 Adhesion of plasma-deposited SiO2 on stainless steel is shown to be enhanced after Ar, N2, and NH3 plasma pretreatments of the substrate. Adhesion is related to the chemical bonding at the interface. Therefore, it is studied by x-ray photoemission spectroscopy XPS and in situ IR ellipsometry performed on very thin lms 30 thick. IR ellipsometry reveals the removal of adsorbed hydrocarbons on the metallic surface by all plasma treatments. XPS measurements show the removal of NOx species, related to the sample electropolishing, using N2 and NH3 plasmas; in contrast, Ar has practically no effect in this case. Plasma-induced modications are not limited to surface cleaning. Some nitrogen is incorporated in the substrate after N2 and NH3 plasmas. In particular, nitrogen is found bonded to Si and to Cr after NH3 and N2 treatments, respectively, we interpret the adhesion enhancement by hardening of the substrate surface region in the case of N2 plasma, while, in the case of NH3, it may be related to the formation of silicon nitride. CrNSi linkages between the substrate and the lm may also contribute to adhesion improvement. We also observed changes in the early stages of the lm growth. A higher sticking coefcient of dissociated species on the surface is revealed after plasma pretreatment. Narrowing of the Si 2 p peak in XPS spectra observed in pretreated samples is attributed to a better ordered SiO2 structure at Si sites in terms of bond angles and/or lengths. In contrast, both IR ellipsometry and XPS show no change at O sites. 1998 American Vacuum Society. S0734-21019804001-9

I. INTRODUCTION SiO2 thin lms on metallic surfaces have many possible industrial applications, such as corrosion resistant layers or adhesion primers for subsequent painting. Plasma-enhanced chemical vapor deposition constitutes a possible alternative solution to replace the chemical baths currently used to grow coatings. The bath efuents can be harmful for the environment. In contrast, in low pressure plasma processes the material quantities involved are low, and recycling of the efuents is less problematic. However, for such applications, good adhesion of the lm to the substrate is necessary. In order to achieve adhesion enhancement, plasma pretreatments of the substrate surface performed in situ immediately before lm deposition appear particularly well adapted. Generally, steel surfaces exposed to air are covered by an adsorbed hydrocarbon contamination layer that arises from the manufacturing process, surface preparation, or simply from the contact with atmosphere.1 Low pressure plasma treatment is efcient for removing the surface contamination.2 Besides hydrocarbon removal also other effects are expected: for instance, in the case of polymers,37
a

depending on the substrate and the plasma used, surface crosslinking or grafting of new chemical species at the surface is generally observed. In our case, modications such as roughness changes and surface nitridation can be expected, as well as modications of the lm structure in the early stages of growth. In the present work, we study the effect of plasma pretreatment in different gases Ar, NH3, N2 on the adhesion of SiO2 lms on stainless steel. We evaluate adhesion using a microscratch test technique2,8,9 and we relate its enhancement to the chemical structure of the interface studied by x-ray photoemission spectroscopy XPS and in situ IR ellipsometry. II. EXPERIMENTAL DETAILS
A. Sample preparation

Electronic mail: drevillo@poly.polytechnique.fr J. Vac. Sci. Technol. A 161, Jan/Feb 1998

Prior to lm deposition, AISI 316L stainless steel substrates were electropolished to make them suitable for ellipsometric and XPS measurements. Samples were then degreased in an ultrasonic bath for 5 min successively using trichloroethylene, acetone, and ethanol. Amorphous hydrogenated silicon dioxide ( a -SiO2) lms were deposited in a dual mode remote plasma reactor.10 The samples face a remote 2.45 GHz microwave plasma, while a
1998 American Vacuum Society 6

0734-2101/98/161/6/7/$10.00

Bertrand et al.: Adhesion improvement of plasma deposited silica

13.56 MHz rf signal is applied to the substrate holder. a -SiO2 was grown from a SiH4 /O2 /Ar mixture at a pressure of 100 mTorr.2 A growth rate of 3 4 s1 was used in order to deposit very thin lms 30 thick, 8 s duration for the XPS study of the interface. However, the deposition system allows growth rates of more than 20 s1 of the same material by changing the pressure and the ow rate. The ratio of oxygen and silane ow rates was xed at 2.5 in order to obtain stoichiometric SiO2 lms. The lm stoichiometry was checked by UV-visible ellipsometry on several tens of nanometers thick lms.2 A low index value 1.34 in UV-visible measurements indicated that the material is relatively porous 30% porosity using Bruggeman effective medium approximation11. Prior to a -SiO2 deposition in the dual mode plasma, the samples were pretreated in ammonia (NH3), nitrogen (N2), or Argon Ar plasmas without exposing them to air. These treatments were performed under nominally the same plasma conditions using a pressure of 100 mTorr, rf power of 160 W, and a rf-induced negative bias of 300 V. The treatment time was 10 min.
B. Adhesion tests

After analyzing broad scan XPS spectra from 1050 to 0 eV, we then study the highly resolved peaks: Cr 2 p , Fe 2 p , O 1 s , C 1 s , Si 2 p , and N 1 s peaks. Spectra were translated to get the C 1 s peaks at 284.8, the observed shifts due to charge effects for 30 thick silica lms being very small smaller than 0.2 eV.

D. IR ellipsometry

An IR ellipsometer is attached to the plasma reactor for in situ measurements, using an angle of incidence of 70. This allows one to determine the effect of plasma pretreatment or to analyze the vibrational properties of the surface chemical groups. The phase-modulated ellipsometer used in this study is based on Fourier transform IR spectroscopy with a resolution of 8 cm1, as described elsewhere.12 The system can record wavelengths from 2 to 11 m and it can reach monolayer sensitivity.13 Ellipsometry14 consists of measuring tan()ei, where and are the ellipsometric angles. The difference in between the substrate covered with a lm and a bare ) gives in the case when d , d is the lm substrate ( thickness, and the wavelength:14 d A 1 Re 1 f

The adhesion was evaluated by the microscratch test MST.9 During the scratching procedure a hemispherical Rockwell C diamond stylus 200 m radius was moved along the surface, while linearly increasing the applied load. A critical load ( L c ) has been determined at which delamination of typically 0.5 m thick lms started to occur as identied by optical microscopy observations. For each specimen, three to ve sctratches were performed and an average L c value was determined. The estimated measuring error is 0.1 N.
C. XPS measurements

In order to probe the lm/substrate interface and the early stages of growth by XPS, it is necessary to deposit SiO2 lms with thickness inferior to the electron escape depth of XPS: thus 30 thick lms were chosen. XPS measurements have thus been performed on a bare substrate and on a -SiO2-covered samples deposited on untreated, Ar, NH3, and N2 pretreated stainless steel. XPS measurements are performed in a Kratos instrument, using Mg K 1253.6 eV radiation, with 40 eV pass energy for broad scans, and 10 eV for high resolution scans. The instrument resolution is about 0.8 eV, and all measurements are performed at electron take-off angles of 90 perpendicularly to the sample surface and at 60. These two angles allow us to probe the material at two different depths, the largest being obtained at 90. The high-resolution spectra are treated by Shirley-type background subtraction, except for the Cr 2 p and Fe 2 p peaks, and normalized to one. A curvetting program is used for peak separation. The program permits variation of the curve parameters, such as the Gaussian and Lorentzian full width at half maximum FWHM and the peak position.
JVST A - Vacuum, Surfaces, and Films

where f is the lm complex dielectric function. A is a constant that does not depend on wavelength because values of dielectric functions for metals are very large. Vibrational modes with large enough strength are split into two components in the IR spectra: the transverse optical TO mode and the longitudinal optical LO mode.1517 Under oblique incidence, the LO mode is easily observed18 on metal, while the TO mode is much more difcult to detect. In our case, d , the presence of a vibrational mode, TO or LO, is indicated by an inexion point in .2 The lm, in all cases, is modeled in ellipsometric simulations as a homogeneous and uniform layer on stainless steel with an abrupt interface.

III. RESULTS AND DISCUSSION

A. Adhesion enhancement

Treatments by N2, NH3, and Ar rf plasmas were performed on the metal surface previously chemically degreased. About 5000 thick SiO2 lms were grown immediately after the pretreatment. The results obtained by the MST measurements are shown in Fig. 1. It is observed that all pretreatments were efcient to enhance a -SiO2 adhesion, with L c of 2.08, 2.38, and 2.40 N after Ar, NH3, and N2 treatments, respectively, compared to the untreated sample ( L c 1.49 N). Keeping in mind that the estimated precision of the microscratch test is 0.1 N, the L c values for N2 and NH3 plasmas are found larger than that for Ar plasma.

Bertrand et al.: Adhesion improvement of plasma deposited silica

TABLE I. Atomic concentrations at. % as determined from XPS measurements at 90 incidence angle. Element Cr Fe O Si N C Bare 6.8 5.5 45.7 13.9 28.1 Untreated 2.2 4 58.3 19.1 5.4 10.9 Ar 2.6 2.4 57.6 23.4 5.2 8.8 NH3 1.1 2.1 60.5 25.8 3.4 7.1 N2 0.4 0.8 59.3 29 1.2 9.4

FIG. 1. Critical load values obtained by the microscratch test for different plasma pretreatments.

B. Plasma cleaning

Air-exposed stainless steel is covered by a native oxide layer from 10 to 50 thick composed of metal oxides and hydroxides.1924 A layer of adsorbed hydrocarbons is generally present on top of the oxide.1,19,2325 Moreover, despite their cleaning effect, some organic solvent molecules from the chemical degreasing procedure are also likely to stay on the surface, as well as adsorbed water molecules.19,23,26 In the present study the removal of hydrocarbons from the surface by plasma treatments is monitored by in situ IR ellipsometry performed in the region from 2800 to 3100 cm1. This range contains the symmetric ( 2855 cm1) and asymmetric ( 2925 cm1) CH2 and symmetric ( 2870 cm1) and asymmetric ( 2960 cm1) CH3 vibrational stretching modes.27 Ellipsometric spectra were measured before and af values ter Ar, N2, and NH3 plasma treatments and the for treated and for untreated were calculated. In Fig. 2, the removal of CHn -containing species is revealed by inex . It appears that the untreated surface is ion points in covered by a CHn -containing layer that disappears after a few seconds of plasma treatment. The three types of treatments have a similar effect, and no detectable presence of CHn species is seen on the surface after treatment. Using the

strength in Lorentz model for CH2 in polyethylene,28 we estimate that the thickness of the removed hydrocarbon layer is about 510 . The XPS C 1 s peaks are not displayed here. Comparing all a -SiO2 covered samples, Table I tends to conrm the cleaning of hydrocarbon by plasma treatments; the larger C concentration measured at 60 angle not shown here suggests that organic contamination is mostly located on top of the silica lm, and not at the interface. XPS does not seem relevant to monitor cleaning because XPS measurements are performed ex situ. The high C relative concentration found in Table I for the bare substrate would, however, suggest that the thickness of hydrocarbon contamination could be underestimated in IR ellipsometry using polyethylene data. This thickness would be, according to Table I, closer to a few nanometers.
C. XPS measurements

in the range corresponding to CH group vibrational modes. FIG. 2. n Modes are revealed near 2860, 2930, and 2960 cm1 by inexion points. J. Vac. Sci. Technol. A, Vol. 16, No. 1, Jan/Feb 1998

The overall elemental composition determined by XPS on differently treated and SiO2-coated steel substrates is summarized in Table I. One can see that the bare substrate surface is heavily oxidized, and it is contaminated by a layer of hydrocarbons. From Table I, one can observe that Cr concentration compared to Fe is higher than expected in the external layers. Indeed, the alloy contains 18% Cr and 72% Fe, whereas Cr/Fe is larger than 1/4 from XPS measurements. Therefore Cr may play an important role in interface phenomena. The excessive oxygen and nitrogen concentrations may be attributed to the electropolishing process used for sample preparation, in particular the chemical bath containing HNO3. After depositing a thin SiO2 layer untreated sample the surface is covered by the SiO2, but one can still see residual contamination of the surface by C, O, and N Table I. When SiO2 deposition is preceded by plasma pretreatment the surface chemistry and energies change appreciably: we observe a higher silicon concentration, subsequently increasing when Ar, NH3, and N2 plasmas are used. This suggests that an increasingly thicker layer of SiO2 is deposited after treatment in these gases, which may be attributed to a higher sticking coefcient of dissociated species on the surface. It appears that the N2 plasma treatment is most effective in surface cleaning, which in turn has most signicantly contributed to enhanced adhesion see Fig. 1. More efcient cleaning is also indicated by the progressively lower N concentration.

Bertrand et al.: Adhesion improvement of plasma deposited silica

FIG. 3. Cr 2 p normalized peak for untreated, NH3 and N2 treated samples. The background was not subtracted.

FIG. 4. Fe 2 p normalized peak for untreated, NH3, and N2 treated samples. The background was not subtracted.

The results described above point to important chemical effects at the SiO2/metal interface. To get more insight, we performed high resolution XPS analysis; the results are shown in Figs. 36, and the peak assignments are summarized below. Because of the nonuniform shape of the background, we did not attempt to curve t the high resolution spectra of the metals involved: the Cr 2 p and Fe 2 p peaks after different pretreatments are illustrated in Figs. 3 and 4, respectively. For the untreated sample, both peaks contain a metallic component, around 574.0 eV for Cr19,29,30 and around 707.0 eV for Fe.19,31,32 In addition, a broad dominant peak around 3 eV in width is found due to metal oxide around 577.0 eV for Cr2O323,29,33 and around 711 eV for Fe2O3. 3032 The large width of the metal oxide peaks is due to multiplet resonance29 and inhomogeneous oxidation states for example, CrO2, 33 FeO,30 and metal hydroxides. Samples 1 and 3 exhibit the same results as Sample 2. Following plasma pretreatment using NH3 and N2, the metallic component is suppressed. The peaks due to oxidized states do not change appreciably, except for a slight shift to a lower binding energy by 0.5 eV observed in the Cr 2 p peak ( 576.5 eV) and N2 plasma exposure N2 treatment in Fig.
JVST A - Vacuum, Surfaces, and Films

3. This shift is attributed to CrN bonds for pure CrN, the corresponding peak appears at 575.5 eV30,34. Presence of CrN bonds is further conrmed by the structure of N 1 s spectrum see below. The Si 2 p peak around 103.4 eV corresponds to a stoichiometric SiO230,35 Fig. 5. However, the peak width decreases in the following sequence: 2.3 eV, 2.2 eV, 2.0 eV, and 1.9 eV, corresponding to untreated, Ar, NH3, and N2 treated samples, respectively. This point will be discussed below. In the case of NH3 treatment, a small contribution to the Si 2 p peak is observed at 101.6 eV due to SiN bonds in Si3N4. 30,36 XPS measurements performed at a take-off angle of 60 do not show such shoulder. This indicates that the SiN bonds are preferably located at the SiO2/metal interface, as also revealed by the N 1 s peak structure see below. Evolution of the N 1 s spectrum with different treatments is illustrated in Fig. 6. On the bare substrate we can observe peaks due to NO3 and NOx groups centered around 407.5 eV30,37 and 403404 eV,19,30 respectively. When a SiO2 layer is deposited untreated, a small NHx component around 400 eV38 has appeared, probably due to surface contamination. The shape of the peak does not change when Ar plasma is used as shown in Fig. 6, even if some additional

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FIG. 5. Si 2 p normalized peak for untreated, NH3, and N2 treated samples.

surface cleaning may have occurred. However, substantial chemical restructuring at the interface is seen following NH3 and N2 plasma pretreatments. One can still distinguish a small contribution due to NO3 and NOx groups, but the features at lower binding energies in Fig. 6 become dominant. For the NH3 treated sample, new NHx , NSi, and NCr or NFe appear around 399.9 eV,38 397.8 eV,36 and 396.3 eV,39 respectively. For the N2 treated sample, NSi and NCr or NFe are indicated by peaks at 397.7 eV and 396.4 eV, respectively, while the peak at 399.4 eV is attributed N2 from nitridation by N2 plasma.39 A quantitative evaluation of the number of grafted N atoms would not be reliable since XPS measurements are performed ex situ and our in situ IR equipment cannot probe NSi and NCr bonds. Moreover, N atoms already present on the surface due to electropolishing could not be distinguished from grafted N atoms. According to Table I, less nitrogen is detected at the interface following N2 plasma pretreatment, as compared with NH3 plasma. But both plasmas induce the creation of NSi and NCr NFe linkages, which may contribute to covalent bonding between the lm and the substrate, possibly resulting in enhanced adhesion. For the bare substrate, the O 1 s peak not displayed here can be tted with two components around 530.0 and 531.5
J. Vac. Sci. Technol. A, Vol. 16, No. 1, Jan/Feb 1998

FIG. 6. N 1 s normalized and reconstructed peak for all samples measured by XPS.

eV due to metal oxides24,30,31,40 and hydroxides30,32,40,41 or CO bonds42, respectively. After lm deposition untreated or following any plasma treatment and deposition a new dominant feature due to OSi bonds in SiO2 around 532.8 eV30,43 arises and its width 1.8 eV remains constant as a function of substrate pretreatment; it is then difcult to see if the hydroxide peak disappears. In the latter case, an additional smaller peak found at 530.4 eV is still attributed to metallic oxides beneath the SiO2 layer.
D. IR ellipsometry performed on samples prepared for XPS

As mentioned in Sec. II, IR ellipsometry allows one to observe the LO asymmetric stretching mode in silica, located near 1230 cm1. The measurements performed on untreated, NH3, and N2 treated samples related to the bare sub ) are displayed in Fig. 7. values far from the strate ( vibrational zone for instance near 1900 cm1 are larger for NH3 and N2 treated samples than for untreated samples. We suppose that at 1900 cm1 the same value of f same refrac-

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FIG. 7. IR ellipsometry spectra measured on the same specimens as those measured in XPS, in the case of untreated, NH3, and N2 treated samples. The LO SiOSi vibrational mode is revealed through an inexion point in near 1230 cm1.

tive index holds for all the measured samples. Therefore, for the same process duration, a thicker lm is deposited after NH3 and N2 plasma treatments than in the untreated case see 1. The latest result agrees with the XPS data see Table I. The amplitude of resonance is slightly larger after plasma treatment; this may be due to differences in the thickness since the vibration observed for NH3 and N2 treated samples has the same width as for the untreated sample in Fig. 7.
E. General discussion

It is clear from the above that surface preparation is essential to control the surface chemistry and energetics. Weakly adsorbed hydrocarbons involving van der Waals interactions on the air-exposed surface can be removed by plasma treatments that enable a better interaction between the lm and the substrate. Adhesion improvement after Ar plasma is supposed to be mainly due to CHn cleaning. Besides cleaning N2 and NH3 plasmas induce new chemical groups which contribute to chemical linkages at the interface. In addition, the NOx groups are also more easily removed in N2 and NH3 plasmas than in Ar, which in turn results in a better adhesion following the N2 and NH3 treatments. It has been pointed out in Secs. III C and III D that silicon-containing species have a higher sticking coefcient to plasma treated surfaces for the same a -SiO2 deposition conditions. This can be attributed to plasma cleaning which generally leads to a higher surface energy. The present analysis illustrates the advantage of in situ over ex situ techniques. Indeed, it was possible to monitor plasma cleaning of hydrocarbons by in situ IR ellipsometry while XPS measurements were inuenced by a hydrocarbon layer adsorbed on top of silica after the sample exposure to atmosphere. Evolution of the N 1 s peak following both NH3 and N2 plasma treatments suggested formation of metal-nitrogen bonds at the interface. In fact, CrN compounds are known to enhance the surface hardness.44 We summarize that N2 plasma exposure, and to a lesser extent NH3 plasma exposure see Fig. 6, beside surface cleaning, contribute to the surface hardening and mechanical stabilization by nitridation, which nally results in improved adhesion of SiO2 layers. In the case of polymers, surface crosslinking due to intense UV
JVST A - Vacuum, Surfaces, and Films

radiation from plasma has also been reported;3 it substantially increased the cohesion of the near-surface region and improved the adhesion of SiO2 lms.5,6 In the case of NH3 pretreatment, signicant formation of silicon nitride is revealed in Figs. 5 and 6. Some nitrogen is therefore grafted at the interface, but located preferentially in the rst layers of the lm. It can contribute to better adhesion, assuming that silicon nitride adhesion to the substrate is better than SiO2 adhesion. In addition, formation of SiN bonds at the interface, observed after both NH3 and N2 pretreatments, may also contribute to improved adhesion, allowing for the creation of covalent metalNSi bonds. Higher adhesion of plasma-deposited silicon nitride than silicon dioxide lms to c -Si has been observed, and it was attributed to stronger SiNSi bonds.9 In agreement with these results, major contribution of lm-nitrogen-substrate covalent bonds to enhanced adhesion has systematically been determined for dielectric (SiN1.3) and metal Cu, Ag lms on different polymers, including polycarbonate and uorocarbons.7,9 The presence of CrNSi bonds was also proposed to account for SiC lms adhesion enhancement on previously nitrided stainless steel substrates.45 In Fig. 5 the Si 2 p XPS peak width varies with treatment. Broadening, for the untreated sample, induced by variations of Si chemical environment is excluded since the Si 2 p peak remains symmetric around the SiO binding energy. The overall decrease by about 0.5 eV from untreated to N2 treated sample indicates a SiO2 lm with subsequently more ordered microstructure at the Si sites, particularly in bond angles and bond lengths, within the tetrahedral Si network. In Fig. 7 the LO peak width is found the same for all samples. The peak width in vibrational IR modes in amorphous silica is closely related to the SiOSi oxygen bridges bond angles statistical distribution.4648 The TO vibrational frequency, to which the LO frequency is proportional, is indeed a function of this angle, as described for instance by the central force model.48 It was proposed that changes in bond angles modify the electronic distribution on Si and O atoms, inducing a broader distribution of SiO energies in XPS49,50 leading thus to broader O 1 s and Si 2 p peaks; however, this assertion is still controversial.50 Here, as previously mentioned, OSi contribution to the O 1 s peak keeps the same width after pretreatment; this conrms that O sites angle may present a similar statistical distribution within the SiO2 matrix in the three cases. IV. CONCLUSION Adhesion of plasma deposited a -SiO2 thin lms to stainless steel substrate, measured by the microscratch test, has been found to progressively improve following plasma pretreatments in Ar, NH3, and N2. In situ IR ellipsometry and XPS measurements were used to study the mechanisms of adhesion enhancement. In particular, in situ IR ellipsometry allowed us to monitor the plasma cleaning effect through the disappearance of a hydrocarbon contamination layer. XPS results have shown that NO3 groups arising from the electropolishing process are more effectively removed by chemi-

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cally active N2 and NH3 plasmas in contrast to Ar plasma. Exposure to NH3 and particularly to N2 plasmas lead to the formation of metal-nitride groups which in turn induce a larger cohesion of the substrate surface, as compared to the native oxide layer. After N2 and, particularly, NH3 pretreatment, some nitrogen is found in the rst layers of the lm under the form of silicon nitride, which can also explain adhesion enhancement. In addition, creation of metalNSi linkages after N2 and NH3 pretreatments also clearly contributes to the adhesion improvement. Sticking coefcient for the silicon-containing species subsequently increases with pretreatments using Ar, NH3, and N2 plasmas, as indicated by a larger thickness of SiO2, an effect related to a higher surface energy. According to IR ellipsometry and XPS, the lm would exhibit, in the early stages of growth, a better ordered microstructure at the Si sites, whereas bond angle statistical distribution at the O sites does not seem to be affected. ACKNOWLEDGMENTS The authors wish to thank LAir Liquide S.A. for nancial support, particularly Dr. J. C. Rostaing for helpful discussions. The help of Dr. P. Bulkin to monitor surface cleaning and of Dr. R. Etemadi for lm growth was greatly appreciated.
J. E. Castle and D. C. Epler, Surf. Sci. 53, 286 1975. villon, L. Martinu, and J. E. Klemberg-Sapieha, Thin N. Bertrand, B. Dre Solid Films 290 291, 264 1996. 3 villon, F. Poncin-Epaillard, J. E. Klemberg-Sapieha, and S. Vallon, B. Dre L. Martinu, J. Vac. Sci. Technol. A 14, 3194 1996. 4 villon, and F. Poncin-Epaillard, Appl. Surf. Sci. 108, S. Vallon, B. Dre 177 1997. 5 villon, J. E. Klemberg-Sapieha, S. Vallon, A. Hofrichter, L. Guyot, B. Dre L. Martinu, and F. Poncin-Epaillard, J. Adh. Sci. Technol. 10, 1287 1996. 6 villon, A. Gheorghiu, C. Se nS. Vallon, R. Brenot, A. Hofrichter, B. Dre maud, J. E. Klemberg-Sapieha, L. Martinu, and F. Poncin-Epaillard, J. e Adh. Sci. Technol. 10, 1313 1996. 7 E. M. Liston, L. Martinu, and M. R. Wertheimer, J. Adh. Sci. Technol. 7, 1091 1993. 8 J. E. E. Baglin, Fundamentals of Adhesion, edited by L. H. Lee Plenum, New York, 1991, p. 363. 9 L. Martinu, Plasma Treatment and Deposition of Polymers, edited by R. dAgostino Kluwer, Dordrecht 1997, in press. 10 villon, J. Huc, J. Y. Parey, J. C. R. Etemadi, C. Godet, J. Perrin, B. Dre Rostaing, and F. Coeuret, J. Vac. Sci. Technol. A 15, 320 1997. 11 D. A. G. Bruggeman, Ann. Phys. Leipzig 24, 636 1935. 12 villon, Rev. Sci. Instrum. 64, 2153 A. Canillas, E. Pascual, and B. Dre 1993. 13 villon, Rev. Sci. Instrum. 66, 3269 S. Vallon, E. Compain, and B. Dre 1995. 14 villon, Prog. Cryst. Growth Charact. Mater. 27, 1 1993. B. Dre
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