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Abstract:

Nano-crystalline tungsten nitride thin films are synthesized on AISI-304 steel at room temperature using Mather-
type plasma focus. The surface properties of exposed substrate against different deposition shots are examined for
crystal structure, surface morphology and mechanical properties using X-ray diffraction (XRD), atomic force
microscope (AFM), field emission scanning electron microscope (FESEM) and nano-indenter. The XRD results
show the growth of WN and WN2 phases and the development of strain/stress in the deposited films by varying the
number of deposition shots. Morphology of deposited films shows the significant change in the surface structural
with the change in ion energy flux (no. of deposition shots). The change in the ion energy flux results in the
development of strain/stress in the deposited films that leads to improvement of hardness of deposited films.
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3. X-Ray Diffraction results

Fig. 4.1 shows the XRD spectra of the thin coatings synthesized on the stainless steel substrate for 10, 20 and 30
focus shots along with the unexposed sample as reference. The distance between the anode tip and substrate sample
was kept constant at 8 cm, moreover the substrate sample is exposed for the various focus shots and placed the
substrate at room temperature for deposition purpose. Therefore, room temperature deposition is employed which is
suitable for many substrates to be used in the plasma focus chamber for deposition purposes. The XRD results of the
unexposed sample indicate the presence of three peaks that are consistent with the plane reflections (111), (200) and
(220). The XRD results indicate the presence of crystalline phases of WN2 (104), (009), (113) and WN (111) for
different number of focus shots. These results are corresponds to the reference card numbers [01-075-0998, 01-025-
1256]. Evolution of the WN phases on the substrate surface confirms the presence of tungsten nitride thin film on
the substrate surface. The substrate sample after deposition shots shows the new peak related to WN2 (113) plane
and the intensity of the peak varies with the change in the number of focus shots with a very prominent peak shift as
already present in the untreated samples towards the lower angle shift. XRD results represent the new peaks of WN2
(104), WN2 (009), WN (111) plane reflections. There is a shift towards the low angle which might be due to the
incorporation of ions into the lattice sites as a result a large expansion is observed. The energetic ions when interact
with the sample surface it can deeply penetrate into the surface layer which leads to the increase in the local
temperature that enhances the chance to adatom mobility or increase in the strain energy that is suitable for the
crystal growth. As compare with the peaks present in the unexposed samples the new peaks at the same place are
much broader. The XRD results show the intensity of WN2 (113) peak enhances with the increase in the number of
focus shots. It is known that the intensity of the peak is directly related with the crystal phase that increases with the
increase in the WN2 (113) phase with the increase in the number of shots. The effect of various deposition shots on
tungsten nitride phases, their intensities, position and d-spacing are presented in Table 1. The incorporation of the
energetic ions of nitrogen in to the lattice places is responsible for the enhancement of the d-spacing and broadening
of the peak. The peak broadening shows the crystalline size of the tungsten nitride thin films is small. And at higher
number of focus shots the intensities of the peaks related to the tungsten nitride phases increases and the XRD
results shows the decrease in the substrate peaks. The increase in the peak intensity of the nitrides and decrease in
the stainless steel-AISI 304 reflection planes indicates the deposition of tungsten nitride thin films that increases
with the increase in the number of shots. The XRD results shows the shifting with caparison along with the
reference data that confirms the existence stress and strain in the thin films deposited at the substrate surface. The
presence of the residual stress or strain in the films is may be due to the lattice distortion by energetic ions of
nitrogen that are implanted into the interstitial position and create the lattice defects as well as thermal shocks to the
surface of the exposed substrate. Ion implantation in the substrate surface may be responsible to the compressive
stresses while the thermal shocks on the thin film may be responsible to the tensile stresses. The change in the d-
∆𝑑
spacing of the deposited films may leads to the formation of strain ( ) in the deposited film which is calculated by
𝑑
using expression (23).
∆𝑑 𝑑𝑜𝑏𝑠 − 𝑑𝑟𝑒𝑓
=
𝑑 𝑑𝑟𝑒𝑓
Fig. 4.2 indicates that the exposure of substrate sample against 10, 20 and 30 shots generates the residual strain in
the surface of exposed samples. For 10 focus shots, the sample indicates the existence of residual strain in the thin
film deposited on the substrate surface. While the samples exposed against 2o shots indicates the presence of little
tensile strain is in WN (111) and WN2 (009) phases. The strain developed in the deposited films is relaxed at higher
number of focus shots moreover at 30 shots the tensile strain reduces in both phases discussed above. A compressive
strain is observed in WN2 (113) phase when substrate sample is exposed for 10 shots and it relaxes at higher number
of focus shots. When sample exposed for 10 focus shots then WN 2 (104) phase indicates the presence of
compressive strain and on at 20 shots it changes to the tensile strain while on further increasing the focus shots it
transfer again into compressive strain.
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1400

WN2(009)

WN (220)
1200

WN2(116)
WN2(101)
1000

Intensity (a.u.)
800

600 30 Shots

400 20 Shots

200 10 Shots

0 Un Exposed

30 35 40 45 50 55 60 65 70 75 80 85
Position (2 Theta)

Figure 3. XRD spectra of unexposed substrate along with exposed for 10, 20 and 30 deposition shots
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Table 1.
Intensities, d-spacing position and hkl values of various tungsten nitride phases observed at 10, 20 and 30 deposition
shots.

Deposition Parameter phase (hkl) 2θ dobs (Å) Intensities (cps)

Untreated S. Steel 111 42.865 2.10982 461.269
AISI-304 200 50.204 1.81725 450.313
220 74.150 1.27775 528.816
10 shots WN2 104 42.467 2.12869 235.563
009 49.842 1.82959 196.105
113 67.036 1.39442 104.64
WN 111 73.297 1.29156 101.009
20 shots WN2 104 41.919 2.15523 334.56
009 49.309 1.84812 181.579
113 66.971 1.39562 109.872
WN 111 72.520 1.30239 101.01
30 shots WN2 104 42.500 2.12709 200.922
009 49.810 1.83070 269.738
113 66.923 1.39650 148.495
WN 111 73.460 1.28803 95.068
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0.016
WN2 (104)
0.014 WN2 (009)
0.012 WN2 (113)
WN (111)
0.010
0.008
Residual Strain
0.006
0.004
0.002
Tensile
0.000
-0.002
Compressive
-0.004
-0.006
10 20 30
Number of Deposition shots

Figure 4. Residual strain of exposed for 10, 20 and 30 deposition shots

4. Surface Morphology Results

4.1 FESEM graphs

The surface morphology of nano-structured tungsten nitride thin films deposited with different 10, 20 and 30
number of deposition shots along with unexposed substrate is shown in Fig. 5. Some structures are visible on
unexposed substrate surface which may be developed during polishing process. The FESEM results of substrate
surface exposed for 10 shots, show nearly round shape and well ordered grains. The grains having distinct
boundaries with sharp edges are smoothly deposited on the substrate surface. The grains are well compact and
uniformly distributed exhibiting smooth deposition of thin film. The grains of various sizes can be observed on
surface of deposited films. The grains of average size are homogeneously spread over the whole film. The substrate
exposed for 20 focus shots shows that the grains start agglomerating on the surface. The agglomerates of various
shapes can be seen in graph with the development of some cracks and voids on the surface of deposited film. The
grains present in these agglomerates have no well-defined boundary and cannot easily be distinguished from one and
other. The surface morphology of substrate exposed at 30 shots shows that the surface of under laying layer is
smooth and uniformly distributed over the whole surface with agglomeration on the surface. These round shape
agglomerates are well developed having distinct, sharp boundaries. Such structures of the films are expected by the
film deposited by plasma focus device. Energetic nitrogen ions from plasma focus can penetrate deeper into the
substrate surface and increase the local temperature that leads to increase in adatom mobility or high strain energy.
These agglomerated grains various size while average size of these agglomerated grains is around 170±10 nm while
the increase in the agglomeration may increase the surface roughness.
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Figure 5. FESEM graphs of substrate exposed for 10, 20 and 30 deposition shots

5. Mechanical Properties

Improved hardness/elastic modulus is significant characteristic of hard deposited films. Nano Indenter is employed
to analyze the hardness (GPa) of exposed substrate. Figure 8 shows the hardness of exposed substrate for various
(10, 20 and 30) deposition shots along with unexposed substrate. The substrate sample exposed for 10 deposition
shots shows significant increase in the hardness as compared to the unexposed while the hardness of the exposed
sample for 20 shots shows much greater hardness value at the surface of exposed samples and it decreases with the
increase in the depth. The hardness of exposed sample for 30 shots shows almost the same depth profile throughout
with little variation. Figure 9 shows the hardness of exposed sample for various (10, 20 and 30) shots at different
depths of deposited film. Graph shows the maximum hardness of exposed samples at the top surface. The hardness
of sample exposed for 10 and 20 shots increases at the penetration depth (25 nm) and maximum hardness is
7|Page

observed for 20 focus deposition shots and on further increase in the number of deposition shots (i.e. 30 shots) it
decreases. The graph shows the hardness of exposed substrate at different (25, 50, 75, 100 and 800 nm) penetration
depths. In general the hardness of exposed substrate decreases with the increase in the penetration depth and the
maximum value is observed at the top surface of exposed samples. The modulus of exposed substrate is present in
Fig. 10. It shows that the modulus of the deposited film increases with the increase in the number of deposition. The
elastic modulus qualitatively follows the enhancement of the hardness of the hard coatings. With the increase in the
number of deposition shots, the elastic modulus increases.

22

20

18

16
20 Shots
Hardness (GPa)

14
30 Shots
12

10

6 10 Shots

4
Un exposed
2

0 100 200 300 400 500 600 700 800 900

Displacement into Surface of Deposited Film (nm)

Figure 8. Hardness of samples treated with various deposition shots

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25 nm
18
50 nm
75 nm
16
100 nm
800 nm
Hardness (GPa) 14

12

10

2
0 10 20 30
Number of Deposition Shots

Figure 9. Hardness of samples at different depths of exposed samples for different shots
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600
un-exposed
550
10 shots
20 shots
500
30 shots
Elastic Modulus (GPa)

450

400
30 Shots
350 20 Shots

10 Shots
300

250 Un-exposed

200

0 100 200 300 400 500 600 700 800 900

Displacement into Surface of Deposited Film (nm)

Figure 10. Modulus of samples exposed for 10, 20 and 30 deposition shots
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6. Conclusion

The combination of tungsten nitride nano composite films steel was accomplished using
energetic N2 ions of plasma focus device. The samples were exposed to the different deposition
shots and then analyzed structural, surface morphological and mechanical properties. The XRD
spectra show the development of WN phases (WN2 and WN) on the Steel substrate exposed for
10, 20and 30 deposition shots. SEM results show that nano structured grains are similarly spread
over the substrate surface. The SEM graph of substrate showing for 10 shots shows
nanostructure grains which are uniformly spread over the whole surface. The average grain size
experiential in SEM graph is 45±10 nm. In SEM graphs of exposed samples for 20 and 30 shots,
the result of grain agglomeration can be seen by increasing the nitrogen ion energy dose (number
of deposition shots). Maximum agglomeration is observed for 30 deposition shots with the size
of agglomerated species around 180±20 nm. The surface topography of sample showing for 10
deposition shots was studied using SEM which shows rough and uneven topology the roughness
of the exposed substrate increases with the increase in the number of focus shots and maximum
roughness was observed as ~52.2 nm at 30shots. Nano indentation results of exposed sample
shows the enhancement in the hardness of substrate with the increase in the ion energy dose. The
hardness and the surface roughness values of exposed samples for different deposition shots is
higher than the unexposed sample which confirms the deposition of tungsten nitride films on the
substrate surface. The phase analysis, grain size and roughness SEM value of exposed sample
shows the formation of nano-structural tungsten nitride thin film on the substrate using plasma
focus device.
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REFFRENCES:

(1) Toth, L.E., Transition metal carbides and nitrides; Editor Ed.^Eds.;1971.
(2) Yamamoto, T.; Kawate, M.; Hasegawa, H.; Suzuki, T., Effects of nitrogen concentration
on microstructures of WNX films synthesized by cathodic arc method. Surface and Coatings
Technology 2005, 193, (1–3), 372-374.
(3) Polcar, T.; Parreira, N.M.G.; Cavaleiro, A., Tribological characterization of tungsten
nitride coatings deposited by reactive magnetron sputtering. Wear 2007, 262, (5–6), 655-665.
(4) Polcar, T.; Parreira, N.M.G.; Cavaleiro, A., Structural and tribological characterization of
tungsten nitride coatings at elevated temperature. Wear 2008, 265, (3–4), 319-326.
(5) Tsai, M.H.; Sun, S.C.; Chiu, H.T.; Chuang, S.H., Metalorganic chemical vapor deposition
of tungsten nitride for advanced metallization. Applied Physics Letters 1996, 68, (10), 1412-
1414.
(6) Chang, K.-M.; Yeh, T.-H.; Deng, I.-C., Nitridation of fine grain chemical vapor deposited
tungsten film as diffusion barrier for aluminum metallization. Journal of Applied Physics 1997,
81, (8), 3670-3676.
(7) Bystrova, S.; Aarnink, A.A.I.; Holleman, J.; Wolters, R.A.M., Atomic Layer Deposition
of W1.5N Barrier Films for Cu Metallization: Process and Characterization. Journal of the
Electrochemical Society 2005, 152, (7), G522-G527.
(8) Bong, S.; Lee, Y.-J.; Hwang, J.-S.; Park, C.-O., Properties of reactively sputtered WNx as
Cu diffusion barrier. Thin Solid Films 1999, 348, (1–2), 299-303.
(9) Migita, T.; Kamei, R.; Tanaka, T.; Kawabata, K., Effect of dc bias on the compositional
ratio of WNX thin films prepared by rf-dc coupled magnetron sputtering. Applied Surface
Science 2001, 169–170, (0), 362-365.
(10) Soto, G.; de la Cruz, W.; Castillón, F.F.; Dı́az, J.A.; Machorro, R.; Farıá s, M.H.,
Tungsten nitride films grown via pulsed laser deposition studied in situ by electron
spectroscopies. Applied Surface Science 2003, 214, (1–4), 58-67.
(11) Hosseinnejad, M.T.; Ghoranneviss, M.; Etaati, G.R.; Shirazi, M.; Ghorannevis, Z.,
Deposition of tungsten nitride thin films by plasma focus device at different axial and angular
positions. Applied Surface Science 2011, 257, (17), 7653-7658.
(12) Rawat, R.; Chew, W.; Lee, P.; White, T.; Lee, S., Deposition of titanium nitride thin
films on stainless steel—AISI 304 substrates using a plasma focus device. Surface and Coatings
Technology 2003, 173, (2), 276-284.
(13) Hussain, T.; Ahmad, R.; Khan, I.; Siddiqui, J.; Khalid, N.; Bhatti, A.S.; Naseem, S.,
Deposition of titanium nitride on Si (100) wafers using plasma focus. Nuclear Instruments and
Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 2009, 267,
(5), 768-772.
(14) Ahmad, R.; Hassan, M.; Murtaza, G.; Waheed, A.; Zakaullah, M., Study of Lateral
Spread of Ions Emitted from 2.3 kJ Plasma Focus with Hydrogen and Nitrogen Gases. Journal of
Fusion Energy 2002, 21, (3), 217-220.
(15) Khan, I.A.; Jabbar, S.; Hussain, T.; Hassan, M.; Ahmad, R.; Zakaullah, M.; Rawat, R.S.,
Deposition of zirconium carbonitride composite films using ion and electron beams emitted from
plasma focus device. Nuclear Instruments and Methods in Physics Research Section B: Beam
Interactions with Materials and Atoms 2010, 268, (13), 2228-2234.
(16) Hassan, M.; Ahmad, R.; Qayyum, A.; Murtaza, G.; Waheed, A.; Zakaullah, M., Surface
modification of AlFe1.8Zn0.8 alloy by using dense plasma focus. Vacuum 2006, 81, (3), 291-
298.
12 | P a g e

(17) Rawat, R.; Lee, P.; Lee, S.; Arun, P.; Videshwar, A., Argon Ion Induced Changes On
Cadmium Iodide Thin Films Using Dense Plasma Focus Device. AIP Conference Proceedings
2003, 669, 343.
(18) Rawat, R.; Srivastava, M.; Tandon, S.; Mansingh, A., Crystallization of an amorphous
lead zirconate titanate thin film with a dense-plasma-focus device. Physical Review B 1993, 47,
(9), 4858.
(19) Sadiq, M.; Shafiq, M.; Waheed, A.; Ahmad, R.; Zakaullah, M., Amorphization of silicon
by ion irradiation in dense plasma focus. Physics Letters A 2006, 352, (1–2), 150-154.
(20) Rawat, R.S.; Chew, W.M.; Lee, P.; White, T.; Lee, S., Deposition of titanium nitride thin
films on stainless steel—AISI 304 substrates using a plasma focus device. Surface and Coatings
Technology 2003, 173, (2–3), 276-284.
(21) Rawat, R., High Energy Density Pulsed Plasmas in Plasma Focus: Novel Plasma
Processing Tool for Nanophase Hard Magnetic Material Synthesis. Nanoscience and
Nanotechnology Letters 2013, 4, (3), 251-274.
(22) Umar, Z.A.; Rawat, R.; Tan, K.; Kumar, A.; Ahmad, R.; Kloc, C.; Chen, Z.; Shen, L.;
Zhang, Z., Hard TiCx/SiC/aC: H nanocomposite thin films using pulsed high energy density
plasma focus device. Nuclear Instruments and Methods in Physics Research Section B: Beam
Interactions with Materials and Atoms 2013.
(23) Rawat, R.; Arun, P.; Vedeshwar, A.; Lee, P.; Lee, S., Effect of energetic ion irradiation
on CdI films. Journal of applied physics 2004, 95, 7725-7730.