Advanced Materials Research Vol.

976 (2014) pp 93-97

Online available since 2014/Jun/30 at www.scientific.net
© (2014) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.976.93

Analysis of hardness, resistivity and corrosion of HfN thin films

fabricated by D.C. sputtering
Ayesha Courrech Arias1,3,a, Leandro García González1,b,
Julián Hernández Torres1,c, Teresa Hernández Quiroz1,d,
Gonzalo Galicia Aguilar2,e
1
Centro de Investigación en Micro y Nanotecnología, Universidad Veracruzana, Calzada Adolfo
Ruiz Cortines No. 455, Fraccionamiento Costa Verde, CP. 94294, Boca del Río, Veracruz, México
2
Unidad Anticorrosión, Instituto de Ingeniería, Universidad Veracruzana, Av. S.S. Juan Pablo II s/n
Zona Universitaria, Fraccionamiento Costa Verde, C.P. 94294, Boca del Río, Veracruz, México
3
Maestría en Ingeniería de Corrosión, Instituto de Ingeniería, Universidad Veracruzana, Av. S.S.
Juan Pablo II s/n Zona Universitaria, Fraccionamiento Costa Verde, C.P. 94294, Boca del Río,
Veracruz, México
a
acourrech@uv.mx, bleagarcia@uv.mx, cjulihernandez@uv.mx, dterhernandez@uv.mx,
e
gogalicia@uv.mx

Keywords: Sputtering, hafnium, resistivity, polarization resistance

Abstract. The films of hafnium nitride (HfN) have been little explored so it is important to continue
the study of their chemical, mechanical and electrical under different synthesis conditions. In this
work were produced hafnium nitride films (HfN) by DC sputtering. In the deposition chamber was
varied using a flow of nitrogen gas ratio Ar/N2 10, 6.66, 5.4 and 3.33. The obtained films were
characterized by X-ray diffraction, Vickers microhardness, high resistivity measurement package
and tested by D.C. and R.F. electrochemical techniques in order to know their crystalline structure,
hardness, resistivity and corrosion resistance. Electrochemical tests showed that the flow ratio
Ar/N2 = 5 showed maximum polarization resistance, whereas the sample in relation Ar/N2 = 4
showed less resistance value of polarization. All results establish that a good material HfN to be
used as a diffusion barrier in electronic devices.

Introduction
The titanium nitride and chromium metal are widely used in the world due to its chemical and
thermal properties, reflected in the crystallinity, the optical and the decorative material. The
manufacture of the transition metal nitrides is performed through various methods, however
techniques for physical vapor deposition is obtained homogeneous thin films [1,2]. HfN is an
excellent material compared to commercial nitrides TiN and CrN due to its high melting point
(3387 ° ≈) [3], good electrical resistivity that is used as diffusion barrier [4,5], high mechanical
properties, excellent wear resistance and HfN could be formed more rapidly than TiN or TaN
according its formation heat [6]. Also HfN shows a B1-NaCl crystalline structure gives low
resistivity [6].
In this work HfN thin films fabricated by DC sputtering in an atmosphere of Ar/N2 variable. Each
film were evaluated their mechanical, structural, electrical resistivity properties and electrochemical
test was conducted with 3.5 wt% NaCl in a three electrode cell to determine their ability to inhibit
corrosion in the stainless steel 304 (CR).

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP,
www.ttp.net. (ID: 148.247.69.117, CINVESTAV IPN, Mexico, Mexico-08/07/14,17:52:52)
94 Science and Materials Engineering IV

Experimental Procedure
Fabrication

HfN thin films of thickness ≈0.25 µm were fabricated on 304 stainless steel substrates. The
substrates were cleaned with successive rinses in ultrasonic baths in water with phosphate-free
detergent, xilenos, acetone and ethanol in order to clean surface and remove grease. Deposition
process performed by an Sputtering System V3 (Intercovamex) occupying a Hafnium target (99.9
% pure) DC power source applying 150 W at 20 sccm of high-purity Argon flux (99.99% pure) and
2, 3, 4, 5 and 6 sccm of nitrogen flux (99,99% pure) obtaining an Ar/N2 ratio inside deposition
chamber of 10, 6.66, 5, 4 and 3.33, respectively. Thickness thin films were estimated by SQM-160
Monitor with a gold disc into chamber and records thickness value according time and rate
deposition.

Characterization
a) X-Ray Diffraction
Crystalline phases were identified by X-ray diffraction by using a D8 Advance-Bruker with Göbel
mirror-parallel beam as primary optics and scintillation detector. Incidence angle was 1º and 2θ
from 20º up to 80º using Cu kα1 radiation at 40 kV and 40 mA and 1 mm aperture slit was used.

b) Vickers Microhardness testing

Hardness was evaluated by Vickers Microhardness test machine (HM-124 Mitutoyo) applying loads
as of 0.001 up to 0.5 kgf and it was necessary to apply an Koursunsky indentation model [7] to
provide a fit to experimental data and let us to know actual hardness value of films (Equation 1).

= + Eq. 1

Where HTot is total hardness, Hs is substrate hardness, Hf is film hardness and β is relative
indentation depth and is calculated by Equation 2.

= Eq.2
∗

d is the average diagonals of Vickers Microhardness evaluation and t is the thin film thickness.

c) Electrical resistivity testing

Electrical resistivity of films was measured by using a high resistivity measurement package
(KEITHLEY, mod. 8009) applying voltages of 2, 5, 10 and 15 Volts.

d) Polarization Resistance
Preliminary electrochemical test was performed by Gamry Potenciostat/Galvanostat/ZRA
Reference 600 applying a DC technique as Polarization Resistance (± 20 mV and scan rate of
1mV/s) occupying three electrode cell: a satured calomel electrode (SCE) as reference electrode, a
graphite rod as counter electrode and sample as working electrode, as electrolyte was used a
solution of NaCl at 3.5%, considering an exposition area of 1.54 cm2.

Results
Fig. 1 shows the X-ray diffraction data from the five samples with Ar/N2 rate from 3.3 to 10. The
X-ray pattern shows diffraction lines characteristic of HfN phase (ICDD Number: 00-033-0592)
with a face-centered cubic structure and theorical lattice parameter a= 4.5253 nm. The decrease in
the Ar/N2 ratio reduces the intensity of the HfN peak until disappear favoring the formation of the
 Advanced Materials Research Vol. 976 95

HfO2 amorphous phase (ICDD Number: 01-089-6225). However, the presence of the HfO2
amorphous phase is not discarded in films obtained in high Ar/N2 ratio. The formation of hafnium
oxide is due to reaction between Hf and residual oxygen in sputtering vacuum chamber, as it has
been reported [4]. However, XRD measurements showed that the peak positions of the thin films
were located at 2θ values below the standard positions of the HfN phase, which suggested an
increase of tensile stress due to the hindered annihilation of point defects, thus increasing lattice
distortion.

Figure 1. XRD pattern of samples

Figure 2 shows a comparison between hardness and electrical resistivity behavior in function of
Ar/N2 ratio. It is observed a maximum value of Vickers microhardness at Ar/N2 ratio = 10. This
hardness values is higher than those reported in literature by Chen et. al. 12.8 GPa [8]. However, it
is observed that the hardness tends to decrease as Ar/N2 ratio also decreases, which indicates that
the increase in nitrogen flux does not favor high hardness values.
Figure 2 shows electrical measurements of the thin films deposited in function of nitrogen flux. The
maximum electrical resistivity value (3.7 ×1013 µΩ-cm) was obtained at 4sccm (Ar/N2 = 5), higher
than those reported values, 107 µΩ-cm [2]. In these work, the resistivity values are related to
presence of HfN amorphous phase, rich in nitrogen [2].

Figure 2. Hardness and Resistivity in function nitrogen flux

96 Science and Materials Engineering IV

High Resistivity value explains polarization resistance value being that maximum value was
obtained at Ar/N2 ratio = 5, which involve the less current density thus less corrosion rate. All
resistivity values exceed to 1×108 µΩ-cm reported by Yuan et al [9] whereas also temperature range
was varied and 1.8×108 reported by Jeng et. al. [10].
Electrochemical evaluation shows interesting results due to get high resistance polarization
therefore less corrosion rate compared with thin films based on metal transition nitride like TiSiNO
where TiN and TiO2 are present and samples showed resistance polarization values in order to kΩ
[11]. We can be observed electrochemical impedance spectrums of films in Figure 3 which one
shows that thin film at 4 sccm (Ar/N2 = 5) has high impedance i.e. capacitive behavior almost
comparable with organic paint and larger than reported for another nitrides. HfN has not been
studied in corrosion area is therefore this work means a big development in materials research.
1200000
304 SS
Ar/N2 = 10
Ar/N2 = 6.66
Z'' (Ω-cm )

Ar/N2 = 5
2

800000
Ar/N2 = 4
Ar/N2 = 3.33

400000

0 400000 800000 1200000

2
Z' (Ω-cm )
Figure 3. EIS spectra

In the Table 1 presents a summary of properties evaluated.

Table 1. Evaluated Properties Summary
Rate H Resistivity Rp i corr CR
Sample Ecorr (mV)
Ar/N2 (GPa) Ω.cm)
(µΩ Ω.cm2)
(Ω (A/cm2) (mm/year)
304 SS -- 4,0 ≈20 [12] 101,1E3 -292.0 260,3E-9 118,9E-3
S1-N2_2sccm 10 15,6 1,23E+13 2,818E6 -25,24 9,244E-9 1,0728E-4
S2-N2_3sccm 6,66 11,8 7,95E+08 6,262E6 -116,8 4,161E-9 4,8285E-5
S3-N2_4sccm 5 10,6 3,78E+13 12,31E6 -86,79 2,11E-9 2,4564E-5
S4-N2_5sccm 4 10,0 6,97E+12 2.704E6 -24,95 9,634E-9 1,1181E-4
S5-N2_6sccm 3,33 10,4 5,43E+11 9,663E6 -81,82 2,696E-9 3,1298E-5

Conclusions
HfN thin films of 0.250 µm thickness were deposited on 304 stainless steel substrates by D.C.
sputtering. By X-ray diffraction was observed the formation of the HfN crystalline phase at Ar/N2
ratio= 10. However to decrease the Ar/N2 ratio the HfN crystalline phase disappear, remaining only
the HfO amorphous rich in nitrogen, which affected the thin film hardness but favor high electric
resistivity values. Resistivity results were corroborated by the larger polarization resistance values
and this behavior could be the hafnium oxide formation as insulator. The values of the resistivity of
the thin films obtained in this study have not been reported and due to its interesting properties may
have applications as excellent diffusion barriers.
 Advanced Materials Research Vol. 976 97

Acknowledgments
To Consejo Nacional de Ciencia y Tecnología for economical support by project number 154516
and to Ing. Carlos Alberto Florian Aguilar for resistivity measurements.

References
[1] R. Bunshah (Ed.) “Handbook Of Deposition Technologies For Films And Coatings” (Noyes
Publications, Park Ridge, N.J., 1994).
[2] R. Hübler, A. Cozza, T.L. Marcondes, R.B. Souza, F.F. Fiori, Surface And Coatings
Technology, Vol. 142-144, 2001, Pages 1078-1083.
[3] H.O. Pierson, Handbook Of Refractory Carbides And Nitrides. Properties Characteristics,
Processing And Applications, Noyes, New Jersey, 1996
[4] J.-S. Jeng, Chin-Hung Liu, J.S. Chen, Journal Of Alloys And Compounds 486 (2009) 649-652
[5] V.K. William Grips, Harish C. Barshilia, V. Ezhil Selvi, Kalavati, K.S. Rajam, Thin Solid Films
514 (2006) 204-211.
[6] I.Barin, Thermochemical Data Of Pure Substances, 3er. Ed., Vch, New York, 1995
[7] A.M. Korsunsky, M.R. McGurk, S.J. Bull, T.F. Page, Surface and Coatings Technology 99
(1998) 171-183
[8] Chen, Y., Laha, T., Balani, K., Agarwal, A., Scripta Materialia 58 (2008) 1121-1124
[9] Longyan Yuan, Guojia Fang, Chun Li, Mingjun Wang, Nishuang Liu, Lei Ai, Yanzhao Cheng,
Huimin Gao, Xingzhong Zhao, Applied Surface Science 253 (2007) 8538-8542
[10] Chih-Huang Tsai, Yi-Sheng Lai, J.S. Chen., Journal Of Alloys And Compounds 487 (2009)
687-692
[11] Chi-Lung Chang, Chung-Wei Wu, Thin Solid Films 517 (2009) 5219-5223
[12] Sears, Z & Y, Universitary Physics, 2003.
Science and Materials Engineering IV
10.4028/www.scientific.net/AMR.976

Analysis of Hardness, Resistivity and Corrosion of HfN Thin Films Fabricated by D.C. Sputtering
10.4028/www.scientific.net/AMR.976.93

DOI References
[4] J. -S. Jeng, Chin-Hung Liu, J.S. Chen, Journal Of Alloys And Compounds 486 (2009) 649-652.
http://dx.doi.org/10.1016/j.jallcom.2009.07.023
[5] V.K. William Grips, Harish C. Barshilia, V. Ezhil Selvi, Kalavati, K.S. Rajam, Thin Solid Films 514
(2006) 204-211.
http://dx.doi.org/10.1016/j.tsf.2006.03.008
[7] A.M. Korsunsky, M.R. McGurk, S.J. Bull, T.F. Page, Surface and Coatings Technology 99 (1998) 171-
183.
http://dx.doi.org/10.1016/S0257-8972(97)00522-7
[8] Chen, Y., Laha, T., Balani, K., Agarwal, A., Scripta Materialia 58 (2008) 1121-1124.
http://dx.doi.org/10.1016/j.scriptamat.2008.02.012
[9] Longyan Yuan, Guojia Fang, Chun Li, Mingjun Wang, Nishuang Liu, Lei Ai, Yanzhao Cheng, Huimin
Gao, Xingzhong Zhao, Applied Surface Science 253 (2007) 8538-8542.
http://dx.doi.org/10.1016/j.apsusc.2007.04.024
[10] Chih-Huang Tsai, Yi-Sheng Lai, J.S. Chen., Journal Of Alloys And Compounds 487 (2009) 687-692.
http://dx.doi.org/10.1016/j.jallcom.2009.08.040
[11] Chi-Lung Chang, Chung-Wei Wu, Thin Solid Films 517 (2009) 5219-5223.
http://dx.doi.org/10.1016/j.tsf.2009.03.081