Characterization of Polycrystalline Tungsten Surfaces Irradiated with Nitrogen Ions by X ray Photoelectron Spectroscopy

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Characterization of Polycrystalline Tungsten Surfaces Irradiated with Nitrogen

Ions by X-ray Photoelectron Spectroscopy

Yoshitomo Kamiura

1,*

, Kenji Umezawa

1

, Yuden Teraoka

2

and Akitaka Yoshigoe

2

1Osaka Prefecture University, Faculty of Liberal Arts and Sciences, Sakai 599–8531, Japan

2Quantum Beam Science Center, Japan Atomic Energy Agency, SPring-8, Sayo-gun, Hyogo 679–5148, Japan

Polycrystalline tungsten surfaces were irradiated at room temperature with two kinds of nitrogen ions̶N+ and N

2+̶at 2.5 keV by using an ion beam apparatus. Results of X-ray photoelectron spectroscopy (XPS) experiments performed using synchrotron radiation at SPring-8 showed that upon irradiation of the tungsten sample with either kind of ion, the full widths at half maximum (FWHM) of the W 4f7/2 and W 4f5/2 peaks broadened and the peaks at 35.8 eV and 37.8 eV̶which correspond to WO3 binding energies̶increased slightly; this indicated the formation of tungsten nitride at the subsurface below the interface. The N 1s spectra of tungsten after nitrogen ion beam irradiation were decom-posed into four component peaks. The positions of these component peaks were observed to be the same as those of the standard tungsten oxynitride W0.62(N0.62O0.38), which exhibited W2N peaks in X-ray diffraction analysis. The main decomposed peaks at 397.3 eV and 398.1 eV were attributed to W-N bonds and W-N-O bonds, respectively. The variation of the intensity ratio of the N 1s peak at 397.3 eV to the W 4f dou-blet peaks (corresponding to W-N bonds) as a function of the escape depth, which was measured by angle-resolved XPS, apparently followed a normal distribution for the irradiated samples. This indicates that the W-N bond density of the tungsten surface irradiated with N2+ ions is high-er than that of the surface irradiated with N+ ions and also that the N

2+ ions penetrate slightly deeper than the N+ ions. [doi:10.2320/matertrans.M2016107]

(Received June 28, 2016; Accepted June 30, 2016; Published July 29, 2016)

Keywords: polycrystalline tungsten, nitrogen ion beam irradiation, nitridation, oxynitride, X-ray photoelectron spectroscopy

1.  Introduction

Tungsten is a hard metal that possesses good thermal con-ductivity, a high melting point, and a high sputtering thresh-old. Tungsten and its compounds have various uses. For ex-ample, tungsten trioxide (WO3) is an attractive material for

use in electrochromic devices,1) as a catalyst in wastewater

treatment,2) and as a gas sensor.3) It is particularly important

to investigate the oxidation states of the tungsten surface in the case of its use in devices or sensors formed with WO3

films. The compositions and chemical states of these films have been characterized by analytical methods such as X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and electron probe mi-croanalysis (EPMA).4,5) In the case of oxidation of the

tung-sten surface with oxygen plasma, the O 1s and W 4f XPS peak ratios indicate that the stoichiometry of the oxide films is independent of the plasma exposure time and that the chemical composition of the oxide is not related to the lower oxide states but is instead related to the W6+ states. Their

re-sults of ToF-SIMS depth profiles revealed that during plasma oxidation, a higher substrate temperature results in a thicker oxide layer and lower levels of water and hydrogen contami-nations in the film.4)

It has been reported that EPMA is effective in discriminat-ing the chemical states of tungsten and tungsten oxides (WO2,

WO2.72, and WO3) in small areas (i.e., at a resolution of a few

micrometers) and without being affected by the oxidized lay-er at the tungsten surface, which is not the case with XPS.5)

Braun et al.6) studied oxygen vacancy defect states in

WO3−δ/TiO2 (110) films deposited by pulsed laser ablation

from a WO3 target. From the valence band spectra of these

films obtained by synchrotron-based XPS, it was found that

in the as-deposited film, the defect states associated with ox-ygen vacancies originated from the structure in the bulk of the film or from the film-substrate interface region and that the defect states were removed by oxidation during post-anneal-ing.

Research attempts have been made to incorporate oxygen as the second gas during the deposition of transition metal nitrides. Khamseh7) reported that the tungsten oxynitride film

deposited by reactive magnetron sputtering became amor-phous and this film showed better corrosion resistance than the tungsten nitride film in 0.05 M H2SO4 solution.

Studies have also been conducted on the nitridation of tungsten by using XPS, X-ray diffraction (XRD), and scan-ning electron microscopy (SEM). WNx is one of the

promis-ing materials in device fabrication. The use of Cu instead of Al as an interconnection material has accompanied the minia-turization of ultra-large-scale integration (ULSI) devices, and the WNx film can act as a barrier to the diffusion of Cu into a

Si substrate during annealing. WNx films are synthesized

mainly by sputter deposition with a mixture of Ar and N2

gas-es or by atomic layer deposition (ALD), in consideration of compatibility of the deposition method with existing device fabrication methods.8–10) Uekubo et al.8) reported that among

the Si/(W, W2N or WN)/Cu structures, the W2N layer was

the most effective in preventing Cu from diffusing into the Si substrate after annealing at 790 C for 30 min. They deter-mined the diffusion coefficient and activation energy of Cu in W2N by analyzing the time elapsed from the onset of

diffu-sion to Cu silicide formation and demonstrated the potential of the W2N layer as a barrier.8) Baker et al.11) investigated the

deposition process of the W2N film and cathode poisoning

effects by means of reactive sputtering of a pure W target with a mixture of Ar and N2 gases, and their XPS and XRD results

revealed that W2N films were deposited when more than 10%

N2 was used in the sputtering gas and that excess N2 was

in-*

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corporated into the octahedral interstitial sites of W2N.

Given that further miniaturization of ULSI devices and mi-crosensors seems likely in the future, a more detailed charac-terization of transition metal nitride films and oxynitride films is required because the near-surface region up to depths of several nanometers strongly affects the characteristics of de-vices. In the present work, polycrystalline tungsten (poly-tungsten) surfaces with native oxides were irradiated with two kinds of nitrogen ions (i.e., N+ and N

2+) of a defined

ki-netic energy in order to understand the interactions between the transition metal surface and the ions implanted during de-vice fabrication. The chemical states of the near-surface re-gion as formed by the respective ions were investigated by angle-resolved XPS using synchrotron radiation.

2.  Experimental Procedure

2.1 Sample preparation

Each of the polytungsten sheets (W, 99.99%, 15 ×  15 ×  0.3 mm3, Furuuchi Chemical Corporation) was cleaned with

electronic-grade acetone and ethanol for 10 min by using an ultrasonic cleaner and then dried with dry N2 gas. The

tung-sten surfaces were irradiated with N+ and N

2+ beams at

2.5 keV by using an ion beam apparatus. This apparatus com-prised a cold-cathode-type ion source; a Wien filter (E ×  B mass separator); and electrostatic lenses for acceleration, fo-cusing, and deceleration of the ion beam. Nitrogen gas (99.9995%) was introduced into the ion beam apparatus, in which the base pressure was kept below 2 ×  10−7 Pa. The

dose value of N atoms on the irradiated surfaces was estimat-ed using a Faraday cup as being about 2 ×  1016 atoms/cm2 at

room temperature. After being subjected to ion beam irradia-tion, the samples were rapidly transferred to the surface reac-tion analysis apparatus (SUREAC2000) constructed in beam-line BL23SU at SPring-8. In all synchrotron XPS experi-ments, the base pressure was kept below 2 ×  10−8 Pa.

2.2  Analytical methods

The chemical states of each near-surface region of tungsten were investigated by angle-resolved XPS using synchrotron radiation. Under the assumption of the interaction of N+ and

N2+ ions with the tungsten near-surface region, W 4f, N 1s, O

1s, and wide spectra were recorded at a photon energy of 1569.0 eV and at take-off angles of 30 , 40 , 50 , 60 , 70 , 80 , and 90 (surface normal direction). The energy positions in the spectra were calibrated with reference to the Au 4f7/2

peak (binding energy of 83.9 eV) of a thin Au film. In the present experiments, the light polarization vector was not tak-en into consideration, because the surface was polycrystalline in nature.

In addition, the abovementioned spectra were also mea-sured for tungsten oxynitride powder (W0.62(N0.62O0.38),

Ja-pan New Metals Co., Ltd.) by means of an ESCA 850 appa-ratus (Shimadzu) with Mg Kα radiation (1253.6 eV), for the purpose of comparison of the chemical states and composi-tions of the near- surface region. The base pressure during the XPS measurements of this tungsten oxynitride powder was kept below 5 ×  10−7 Pa, and the peak position in its spectrum

was calibrated using the Ag 3d5/2 peak (binding energy of

368.3 eV) of a Ag sample after Ar+ sputtering. The XRD

pro-files of the powder were recorded using the RINT 2500 appa-ratus (Rigaku) with Cu Kα radiation (λ  =  0.154 nm) at an accelerating voltage of 40 kV and tube current of 200 mA.

3.  Results and Discussion

3.1  XPS spectra of tungsten before and after nitrogen ion beam irradiation

Figure 1 shows the W 4f and N 1s spectra of metallic tung-sten before and after separate irradiation with N+ and N

2+ ion

beams, measured at a take-off angle of 90 . The intensities of the lines were normalized using the W 4f7/2 and N 1s peak

heights after linear background subtraction.

In the W 4f spectrum of the non-irradiated tungsten sur-face, the two peaks at binding energies of 31.3 eV and 33.4 eV correspond to the spin-orbit doublet peaks of W 4f7/2 and W

4f5/2, respectively, corresponding to the metallic substrate.

The two weak peaks at higher binding energies, i.e., at 35.8 eV and 37.8 eV, indicate the presence of oxides (WO3).

The full width at half maximum (FWHM) of W 4f7/2 was

measured to be 0.75 eV for the tungsten samples before irra-diation with the nitrogen ion beams, whereas the FWHM val-ues of W 4f7/2 of the tungsten samples broadened to 1.04 eV

and 1.12 eV after irradiation with N+ and N

2+ ion beams,

re-spectively, along with line broadening of the W 4f5/2 peaks

after irradiation. The intensities of the weak peaks at the WO3

binding energies increased after irradiation of the tungsten surface with N+ ions, and this increase was even greater after

irradiation with N2+ ions.

The N 1s spectrum of non-irradiated tungsten showed an asymmetrical peak at 399.7 eV. After irradiation with either of the nitrogen ion beams, the peak at 399.7 eV became a

Fig. 1 XPS spectra measured at θ =  90 for non-irradiated tungsten, as well as for tungsten after its irradiation with N+ and N

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mere shoulder on a new peak that appeared at 397.6 eV. The decrease in the peak at 399.7 eV is attributed to nitrogen ion beam sputtering, and this peak is probably attributable to con-tamination. All these results taken together suggest that nitro-gen ion beam irradiation resulted in the nitridation and/or oxynitridation of the tungsten sample.

3.2 Angle-resolved XPS spectra of tungsten irradiated with nitrogen ion beams

Figure 2 shows the angle-resolved W 4f and N 1s spectra of tungsten after its irradiation with the nitrogen ion beams. In the figure, θ denotes the photoelectron take-off angle. The intensities of the lines were normalized using the W 4f7/2 and

N 1s peak heights. After irradiation with the N+ beam

(Fig. 2(a)), a decrease in the take-off angle to less than 60 resulted in a slight increase in the intensity of the peaks at the WO3 binding energies, owing to an increase in the surface

sensitivity. The area intensity ratio of the W 4f7/2 peak to the

W 4f5/2 peak for a clean tungsten surface is nearly equal to

4/3, which is the degeneracy ratio; however, the area intensi-ty ratio of these doublet peaks was not originally equal to the degeneracy ratio, since the non-irradiated surfaces contained tungsten oxide, as shown in Fig. 1. Moreover, the doublet peaks of the N+-irradiated surface were equal in height at θ = 

50 and θ =  30 (Fig. 2(a)). These results also suggest the ni-tridation or oxynini-tridation of metallic tungsten after its irradi-ation with N+.

After the irradiation of tungsten with N2+ (Fig. 2(c)), the

intensity of the peaks at the WO3 binding energies increased

slightly only at θ =  30 . No change occurred in the intensity ratio of the doublet peaks, in contrast to the results for N+

ir-radiation. The peak at 399.7 eV decreased considerably after irradiation of tungsten with the N+ beam as shown in Fig. 1;

after irradiation with the N2+ beam, the peak and tail at and

over binding energies of 399.7 eV remained in the near-sur-face region. However, the W 4f doublet peaks after N2+

irra-diation were broader than those after N+ irradiation.

There-fore, the N2+-irradiated tungsten surface is considered to have

a slightly higher density of W-N bonds than the N+-irradiated

surface.

Figure 3 shows O 1s spectra measured before and after ir-radiation; during angle-resolved XPS measurements, there was no obvious change in the line shape and FWHM. The intensities differed between the N+-irradiated and the N

2+

-ir-radiated surfaces because of the difference in their sputtering rates. The O 1s spectra before and after irradiation exhibited slightly asymmetrical peaks on the high binding energy side; this is because the oxide states of the W 4f doublet peaks were thought to overlap. The thickness of the oxide layer in the non-irradiated samples was estimated to be approximately 1.9 nm from the intensity ratio of their oxides to the spin-or-bit doublet peaks; this oxide layer might have prevented the observation of the small change in oxynitridation in the O 1s spectra.

3.3 Spectrum decomposition

Decomposition of an XPS spectrum is useful for investi-gating the chemical states after ion beam irradiation. It is nec-essary to consider the doublet peaks of W 4f and their oxide peaks in order to decompose the W 4f spectrum containing their oxide states. The line shapes of these doublets are asym-metric on the high binding energy side owing to excitation of electron-hole-pair states, namely, interactions of the Fer-mi-gas conduction electrons with holes caused by the absorp-tion of X-rays by the core electrons. Therefore, a Doniach– Sunjic profile can be fitted to the recorded line by taking into account the instrumental function.12) However, in the present

case, some peaks attributed to W-N bonds and/or W-N-O bonds were expected to overlap with the W 4f spectrum and Fig. 2 Angle-resolved W 4f and N 1s spectra after irradiation of tungsten

with (a), (b) N+ beam and (c), (d) N 2+ beam.

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prevent its proper decomposition. Accordingly, as a next step, we attempted to decompose the N 1s spectra measured simul-taneously.

Figure 4 shows the N 1s spectra measured at θ =  90 for tungsten irradiated with N+ and N

2+ ion beams, as well as the

decomposed lines. The N 1s spectrum exhibits four peaks: at 397.3 eV (A), 398.1 eV (B), 399.7 eV (C), and 401.6 eV (D) (see Table 1).

The decomposition was performed using a line shape that was assumed to be a product of 60% Gaussian and 40% Lo-rentzian functions (indicated as GL(40) in Table 1) after linear background subtraction. Here, the relative sensitivity factor of the component peaks of the spectrum was assumed to be 1. Table 1 also summarizes the peak fitting parameters used.

3.4  XPS and XRD analyses of tungsten oxynitride pow-der

For assistance in the interpretation of our XPS experi-ments, the N 1s spectrum of the standard tungsten oxynitride W0.62(N0.62O0.38) at θ  =  90 was also measured (Fig. 5(a)).

The peak positions of the four decomposed lines from this spectrum were found to be essentially the same as those for

tungsten irradiated with nitrogen ions as shown in Fig. 4. In addition to XPS data, the XRD profile of W0.62(N0.62O0.38)

was also obtained (Fig. 5(b)), and it revealed peaks attribut-able to W2N.11,13) Since the main XPS peaks at 397.3 eV (A)

and 398.1 eV (B) did not appear before nitrogen ion beam irradiation as shown in Fig. 1, the peak at 397.3 eV (A) is at-tributed to the formation of W2N. Because of the higher

elec-tronegativity of oxygen, a chemical shift toward a higher binding energy is expected to occur as a result of the forma-tion of oxides.14) Furthermore, since it was suggested that the

oxynitride was formed in the near-surface region of tungsten as shown in Fig. 1, the peak (B) at 398.1 eV is attributed to W-N-O bonds.15) It is noteworthy that C 1s peaks were

ob-served in the wide spectra. As shown in Figs. 2(b) and 2(d), the surface sensitivity of the two shoulder peaks (C and D) at 399 eV increased slightly with a decrease in the take-off an-gle. Therefore, the shoulder peaks in the N 1s spectra are con-sidered to be carbon contaminants, in the form of N-C and N =  C bonds.16)

3.5 Intensity ratios of N 1s peak (A) to W 4f doublet peaks corresponding to W-N bonds

Figure 6 shows the variation of the intensity ratios of the N 1s peak (A) to the W 4f doublet peaks as a function of escape depth. The intensity ratios were obtained by considering the relative sensitivity factors17) of the N 1s and W 4f doublet

peaks under the assumption of the photon energy being fairly close to that of Al Kα radiation (1486.6 eV), after correction of data under the acquisition conditions. The inelastic mean free path (IMFP), denoted by λ and expressed in nanometers, of photoelectrons normal to the surface can be calculated us-ing the followus-ing TPP-2M formula of Tanuma et al.18); this

value was calculated to be 2.07 nm for W 4f. Fig. 4 Decompositions (labeled A, B, C, and D) of θ =  90 N 1s spectra

(circles) of tungsten after nitrogen ion irradiation: (a) after N+ irradiation and (b) after N2+ irradiation.

Table 1 Values of parameters used for decomposition of N 1s spectrum.

Component A B C D

Position (eV) 397.3 398.1 399.7 401.6

Line shape GL(40) GL(40) GL(40) GL(40)

FWHM (eV) Irradiated surfaces 1.41 1.70 1.71 2.06 FWHM (eV) W0.62(N0.62O0.38) 1.28 1.58 1.64 1.96

Relative sensitivity factor 1 1 1 1

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λ= 0.1×E E2

p βln(γE)− C

E +

D E2

(1)

with

β=0.10+0.944 E2 p+E2g

−1 2

+0.069ρ0.1, (2a)

γ=0.191ρ−0.50, (2b)

C=1.97−0.91U, (2c)

D=53.4−20.8U, (2d)

U=NVMρ = E2

p

829.4, (2e)

and

Ep =28.8 NM

1 2

, (2f)

where E (eV) is the electron energy; Ep (eV) is the

free-elec-tron plasmon energy; Eg (eV) is the bandgap energy for

non-conductors; Nv is the number of valence electrons per atom or

molecule; ρ (g/cm3) is the bulk density; M is the atomic or

molecular weight; and β, γ, C, and D are parameters. The numerical values of these parameters are listed in Table 2. The IMFP value of the N 1s core-level electron, whose plas-mon energy cannot be estimated, is practically equal to that of W 4f as determined by extrapolation of the escape depth by the universal curve.19)

The escape depth, expressed on the horizontal axis in Fig. 6, is given by the product of the IMFP value and the sine of the angle defined by the analyzer direction and the surface normal in the present experiments. The nitridation rate was

7% for the N+-irradiated sample and 8% for the N

2+

-irradiat-ed sample. The variation of intensity ratios corresponding to the W-N bonds apparently had a normal distribution, and the positions of the interfaces were presumed to be about 1.8 nm for the N+-irradiated sample and about 1.3 nm for the N

2+

-ir-radiated sample because of the asymmetrical profiles result-ing from a decay of photoelectrons due to the oxides. N2+ ions

penetrate slightly deeper into the bulk than do N+ ions. The

kinetic energy of N2+ ions is half that of N+ ions even at the

same accelerating voltage. However, in the irradiation of di-atomic molecule ions as such as N2+, collisional cascade

in-creases considerably. Consequently, the sputtering of native oxide by N2+ ions also increases, and N2+ ions may penetrate

slightly deeper into the bulk than do N+ ions. In any case, it is

presumed that the native oxide is sputtered by nitrogen ions, and nitrogen ions replace some of the oxygen atoms in the oxide, penetrate the interface between the oxide and the tung-sten substrate, and form tungtung-sten nitride in the near-interface region in the substrate. In this way, the change in intensity ratios in the near-surface region can be compared if the pho-ton energy of the synchrotron radiation is adequate. The real depth profiles of nitrogen concentration as a function of es-cape depth will be discussed elsewhere through simulation of the implantation profiles.

Moreover, the composition ratio (A/B, i.e., ratio of compo-nents as indicated in Table 1) for the N 1s spectrum is 1.7 for standard tungsten oxynitride, which is close to the value of 1.6 in the stoichiometry. In contrast, this ratio is 1.1 for N+

-ir-radiated tungsten and 1.0 for N2+-irradiated tungsten.

Conse-quently, it appears that the ionic valence of oxynitride for ni-trogen-ion-irradiated tungsten samples is slightly larger than that for the standard tungsten oxynitride and that W(NO) is formed in the near-surface region.

4.  Conclusions

In this study, in order to understand the interaction between the tungsten surface and the nitrogen ions, we investigated the chemical states of polytungsten surfaces before and after their irradiation with nitrogen ion (N+ and N

2+) beams by

angle-re-solved XPS using synchrotron radiation. Upon irradiation of the polytungsten surface with the nitrogen ion beams, the FWHM of the W 4f peaks broadened and a N 1s peak ap-peared at 397.6 eV with peaks corresponding to reduced con-tamination. With the progress of nitridation of tungsten, the area intensity ratio of the W 4f spin-orbit doublet peaks be-came different from the degeneracy ratio. The N 1s spectrum after the irradiation of tungsten with the nitrogen ion beam was composed of four peaks, out of which the two main peaks were attributed to W-N and W-N-O bonds, and W(NO) was formed at the N+- and N

2+-irradiated surfaces at the applied

accelerating voltage. The nitridation rates for the N+

-irradiat-ed and N2+-irradiated samples were determined to be 7% and

8%, respectively. The variation of the intensity ratios of the N Fig. 6 Variation of intensity ratios of N 1s (A) to W 4f doublet peaks as a

function of escape depth after nitrogen ion irradiation.

Table 2 Values of parameters used in equations (2a)–(2f) for determination of IMFP of W.

M ρ (g/cm3) N

V E (eV) Ep (eV) Eg (eV) β γ C D

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1s peak (A) to the W 4f doublet peaks as a function of the escape depth apparently followed a normal distribution, with the N2+ ions penetrating slightly deeper into the surface than

the N+ ions.

Acknowledgements

We thank Dr. M. Tode for the technical support during the ion beam irradiation experiments. We are also grateful to Dr. H. Ishibashi for assistance with the XRD measurements. The synchrotron radiation experiments were performed at beam-line BL23SU of SPring-8 with the approval of the Japan Atomic Energy Agency (JAEA) and the Japan Synchrotron Radiation Institute (JASRI) (Proposal No. 2010B3806).

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Figure

Fig. 1 XPS spectra measured at θ =  90° for non-irradiated tungsten, as well as for tungsten after its irradiation with N+ and N2+ beams
Fig. 1 XPS spectra measured at θ = 90° for non-irradiated tungsten, as well as for tungsten after its irradiation with N+ and N2+ beams p.2
Fig. 2 Angle-resolved W 4f and N 1s spectra after irradiation of tungsten with (a), (b) N+ beam and (c), (d) N2+ beam.
Fig. 2 Angle-resolved W 4f and N 1s spectra after irradiation of tungsten with (a), (b) N+ beam and (c), (d) N2+ beam. p.3
Fig. 3 Angle-resolved O 1s spectra after irradiation of tungsten with (a) N+beam and (b) N2+ beam.
Fig. 3 Angle-resolved O 1s spectra after irradiation of tungsten with (a) N+beam and (b) N2+ beam. p.3
Fig. 4 Decompositions (labeled A, B, C, and D) of θ =  90° N 1s spectra (circles) of tungsten after nitrogen ion irradiation: (a) after N+ irradiation and (b) after N2+ irradiation.
Fig. 4 Decompositions (labeled A, B, C, and D) of θ = 90° N 1s spectra (circles) of tungsten after nitrogen ion irradiation: (a) after N+ irradiation and (b) after N2+ irradiation. p.4
Fig. 5 (a) N 1s spectrum and (b) XRD profle of W0.62(N0.62O0.38).
Fig. 5 (a) N 1s spectrum and (b) XRD profle of W0.62(N0.62O0.38). p.4
Table 1 Values of parameters used for decomposition of N 1s spectrum.

Table 1

Values of parameters used for decomposition of N 1s spectrum. p.4
Table 2 Values of parameters used in equations (2a)–(2f) for determination of IMFP of W.

Table 2

Values of parameters used in equations (2a)–(2f) for determination of IMFP of W. p.5
Fig. 6 Variation of intensity ratios of N 1s (A) to W 4f doublet peaks as a function of escape depth after nitrogen ion irradiation.
Fig. 6 Variation of intensity ratios of N 1s (A) to W 4f doublet peaks as a function of escape depth after nitrogen ion irradiation. p.5
Fig. 6, is given by the product of the IMFP value and the sine The escape depth, expressed on the horizontal axis in of the angle defned by the analyzer direction and the surface normal in the present experiments
Fig. 6, is given by the product of the IMFP value and the sine The escape depth, expressed on the horizontal axis in of the angle defned by the analyzer direction and the surface normal in the present experiments p.5