IJMR_MK111737 – 9.1.
19/reemers
F. M. Fernandes et al.: Deposition of fine copper film on samples placed internally and externally to the cathodic cage
Fernanda M. Fernandesa , Edglay A. RochaFilhob , Ivan A. Souzab , Igor O. Nascimentob , Rô-
mulo R. M. de Sousac , Edalmy O. Almeidab , Michelle C. Feitora,b , Thércio H. C. Costaa,b
a
Textile engineering department, Federal University of Rio Grande do Norte, Natal-RN, Brazil
b
Mechanical engineering department, Federal University of Rio Grande do Norte, Natal-RN, Brazil
c
Materials engineering department, Federal University of Piauí, Piauí-TE, Brazil
Deposition of fine copper film on samples placed
internally and externally to the cathodic cage
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Hanser - Library on January 28, 2019
The cathodic cage plasma nitriding technique is used for
thin film deposition. As such, the hollow cathode effect on
cage holes is directly related to deposition efficiency. The
objective of this work is to study the influence of the cath-
ode length-to-diameter ratio in the deposition of fine copper
films on samples placed internally and externally to the
cathodic cage, in an argon atmosphere, for 3 h at 420 8C.
Compositional, transmittance and morphological character-
ization of films show copper deposition in all treatments.
However, it was observed that substrate temperatures dur-
ing film deposition influence its morphology. As such, the
For personal use only.
formation of continuous film on internal samples is ob-
served, whereas external samples show uniformally dis-
persed nanoparticles as well as the absence of dense film
on substrates. As far as the length-to-diameter ratio is con-
cerned, the 1.5 ratio presented the highest deposition effi-
ciency.
Keywords: Cathodic cage; Thin films; Copper nanoparti-
cles; Hollow cathode
1. Introduction
Copper is widely used in both the civil and automobile in-
dustries, and in recent years has gained significance due to
its bactericidal properties [1, 2]. However, copper is a me-
tallic material usually used in deposition devices, whether,
physical, chemical or plasma, to test and/or prove the effi-
ciency of the system [3, 4]. Plasma nitriding may be used
for coating surfaces to improve mechanical properties and
resistance to corrosion [5 – 8]. Whilst this technique has
greater advantages versus salt bath and gas nitriding, it does
present disadvantages such as the edge effect, damage
caused by opening of arcs and temperature variances. As
an alternative to reduce these limitations, the active screen
nitriding technique was created [5, 9]. Cathodic cage plas-
ma nitriding (CCPN) derives from this technique [10].
Different to ion nitriding, active species do not interact
directly with sample surfaces when using a cathodic cage.
All the workload is applied to the cathodic cage (CC), and
the luminous discharge is dislocated from samples to a me-
tallic screen in cathodic potential [5, 11]. The cathodic
cage’s function is to generate extra secondary electrons,
confine existing electrons in the electromagnetic discharge,
and uniformly distribute the discharge onto the sample [5,
12]. Samples are positioned on an insulating surface and
maintained at a floating potential or a relatively low polar-
ized potential [5, 11].
Whilst CCPN has been used on a variety of materials
[13 – 15], there is a need to better comprehend CCPN mech-
anisms in order for the process to evolve. Several process
variables, such as temperature [16], gas composition [17]
and cathodic cage configurations [5], have been altered
with the objective of improving both deposition and the re-
sulting substrate. Furthermore, there has been analysis and
discussion around variations to the cathodic cage lid [18]
as well as nitriding through external deposition on cage
holes [19].
With the objective of better comprehending the mecha-
nisms of the deposition of copper films using the cathodic
cage technique, and to study the influence of the cathode
length-to-diameter ratio on deposition, glass samples were
positioned internally and externally to the cathodic cage
and were treated in argon (Ar) atmosphere at 420 8C for 3 h.
2. Experimental procedure
Glass substrates measuring 25 · 37.5 mm and 20 · 25 mm
were used for external and internal deposition, respectively.
In order to improve film adhesion, they were treated in a
10 % potassium hydroxide (KOH) and 90 % distilled water
ultrasonic bath for 10 min, followed by agitation in a 10 %
nitric acid (HNO3) and 90 % distilled water solution for
3 min, and bathed in an acetone p.a ultrasonic bath for
10 min.
Six length-to-diameter ratios, i. e. 0.25; 0.5; 0.75; 1.5;
2.25 and 3, were used. 8 mm diameter holes were main-
tained throughout the cage, with varying lid thicknesses of
2, 4, 6, 12, 18 and 24 mm. Each lid measured 65 mm in dia-
meter and contained 19, 13 mm equidistant holes. The lids
were formed with a pure electrolytic copper (99 % Cu) plate
measuring 2 mm, 4 mm and 6 mm in thickness and the cage
with a plate of 4 mm, a process of machining manufactured
both. Figure 1 illustrates the reactor, cage and sample dis-
positions. The cage measured 70 mm (externally) and
62 mm (internally) in diameter, and 26 mm in height.
The plasma equipment utilized is detailed in [20]. Sam-
ples were positioned inside the cathodic cage under a ce-
ramic disk at floating potential, and outside the cage, at
anodic potential, on the reactor vessel upper flange.
Current and voltage parameters varied as per Table 1, as
the objective was to guarantee a hollow cathode effect in
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 IJMR_MK111737 – 9.1.19/reemers

F. M. Fernandes et al.: Deposition of fine copper film on samples placed internally and externally to the cathodic cage

Table 1. Deposition parameters used for hole confinement.

Sample E0 E2 E4 E6 E12 E18 E24

Lid thickness Untreated 2 mm 4 mm 6 mm 12 mm 18 mm 24 mm
Current (A) 0.28 0.33 0.38 0.46 0.52 0.57
Tension (V) 760 810 780 680 580 520
Power (W) 212.8 267.3 296.4 312.8 301.6 296.4

a Thermo Fisher Scientific Genesys 10 UV Spectrophot-

ometer, whilst Field Emission Gun Scanning Electron Mi-
croscopy (FEG-SEM) images, magnified 20 000 · and
80 000 · , were captured using a Zeiss Auriga 40.
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Hanser - Library on January 28, 2019

3. Results and discussion

Figure 2 depicts both internal (I) and external (O) glass

samples, and clearly shows a change in color on all sam-
ples, confirming deposition in all treatments. Figure 2a de-
picts the glass sample without copper deposition (standard),
Fig. 1. 3D image of reactor used for cathodic cage copper deposition whilst Fig. 2Ob–d show higher translucence, confirmed by
process. the visualization of letters positioned behind the film. Fig-
ure 2Oe and f present a different hue with pigmentation ap-
proximate to that of pure copper. Figure 2Og depicts a tran-
sition between samples. As far as samples placed inside the
cathodic cage are concerned, Fig. 2Ib–g, it is clear that for
all cage thicknesses there was a higher deposition when
For personal use only.

compared to external samples. This is due to the proximity

of internal samples, as well as the 420 8C temperature to
which they were subjected.
The variation in the tonality can be attributed to the dif-
ference in the thickness of the deposited films, that is, the
more the sample is coppery, the more efficient was the de-
position of copper on the sample. However, upon attempt-
ing to analyze the thickness of this film on external samples
via transverse SEM analysis, no film was observed. There-
Fig. 2. Samples (a) EO; (b) E2; (c) E4; (d) E6; (e) E12; (f) E18; (g)
E24 Post-treatment. I = internal and O = external. fore, we sought to understand the deposition kinetics in-
volved. According to Nishimoto et al. [10], the longer the
distance between the sample and the active screen, the
Table 2. Transmittance of the films. smaller the deposited particles. As per Sousa et al. [21],
the substrate temperatures influence continuous, dense film
Sample Transmittance (%)
Internal External formation. As part of the samples were positioned outside
the cage at an average distance of 180 mm, the influencing
E0 85.27 temperature was approximately 65 8C, which may not have
E2 65.91 0.0 been sufficient for the adhesion of copper particles and the
E4 42.63 0.0 consequent formation of dense continuous film as defined
E6 22.74 0.0 by Tentardini [22].
E12 5.08 0.0 In order to quantify film transmittance, which would
E18 21.72 0.0 quantify the effect visualized in Fig. 2, all samples were
E24 38.87 0.0 submitted to transmittance testing. Table 2 shows the aver-
age transmittance results of tested samples and Fig. 3 gra-
phically shows the transmittance values.
On external samples, there is a decrease in the intensity
the holes of the cage lid, in order to ensure more effective of light transmitted. As per Fig. 2, sample E12 showed the
copper deposition and uniformity at process temperature. lowest transmittance documented in Table 2. This may be
The parameters that remained constant were temperature related to film thickness and/or the quantity of copper de-
(420 8C), deposition time (3 h) and argon flow (12 cm3 posited. As far as internal samples are concerned, it was
min–1). not possible to either measure or estimate which had the
Quantitative analysis was performed using a Bruker D2 highest deposition, as none of the samples transmitted light.
Phaser energy dispersive X-ray fluorescence spectrometer Figure 4 illustrates film composition quantitative data
in Bragg–Brentano geometry performing 0,028 min–1 obtained using Energy Dispersive X-Ray Spectroscopy
sweeps from 208 to 908. Transmittance was measured with (EDS) and X-ray diffraction (XRF), showing that, as ob-

2
 F. M. Fernandes et al.: Deposition of fine copper film on samples placed internally and externally to the cathodic cage

served in transmittance results, sample E12 contains the
highest quantity of deposited copper, which leads us to af-
firm that this thickness promotes the highest sputtering in
this technique.
Results obtained from both analyses converge. There is,
however, a difference in the percentage of copper found be-
tween techniques. This is due to the precision of the equip-
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Hanser - Library on January 28, 2019
ment used. Furthermore, EDS measures a smaller percent-
age of a specific area compared to XRF. According to
Silva [23] whose study focused on the deposition of fine ti-
tanium nitride films using two distinct cage lid thicknesses
(1 mm and 10 mm), higher length-to-distance ratios result
in thicker films. However, Fernandes et al. [20] had pre-
viously affirmed that the best length-to-distance ratio for

Fig. 3. Standard sample and treated sample transmittance profiles: (A) external samples, and (B) internal samples.
For personal use only.

Fig. 4. Percentage atomic of copper present in the (A) external samples, and (B) internal samples, according to the XRF and EDS analyzes.

Fig. 5. XRD results of (A) external samples, and (B) internal samples.

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 F. M. Fernandes et al.: Deposition of fine copper film on samples placed internally and externally to the cathodic cage
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Hanser - Library on January 28, 2019
For personal use only.

Fig. 6. SEM images of samples (a) E2; (b) E4; (c) E6; (d) E12; and (e) E18.

copper films deposited on internal glass substrates is 1.5,
because greater ratios promote sputtering over a larger dia-
meter and lower film uniformity.
Using XRD analysis on Fig. 5a samples, copper peaks were
found on E2, E4, E12 and E18 external samples. Samples E2
and E4 also showed copper oxide (CuO) peaks. The presence
of these peaks may be a result of residual gas, such as oxygen,
present in the deposition reactor, as reported in ref. [24] the
presence of CuO, after using magnetron sputtering for cooper
deposition. For this deposition a copper target was used and
an oxygen atmosphere. Because the internal samples E2 and
E4 also showed copper oxide (CuO) peaks, they were not
characterized using XRD, since it was sought to obtain copper
films, which can be visualized in Fig. 5b showing that films on
internal samples were more crystalline, whilst samples E18
and E24 showed the formation of CuO and Cu2O.
Figure 6 shows FEG-SEM micrographs of external sam-
ples. Analysis shows the presence of copper nanoparticles,
confirmed by SEM-EDS analysis in the micro-areas.
Furthermore, sample E12 shows the highest density of these
particles, confirming previous analyses and the affirmation
that continuous, dense film formation is not possible on ex-
ternally treated samples, with only copper nanoparticle de-
position occurring.
Figure 7 illustrates the morphology of deposited copper,
magnified 80.000X. Again, nanoparticles were confirmed

4
 F. M. Fernandes et al.: Deposition of fine copper film on samples placed internally and externally to the cathodic cage

Fig. 8. Transversal morphology of films de-

posited on internal samples.
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Hanser - Library on January 28, 2019

as previously indicated in this work, and affirmed by Nishi-

moto et al. [9]. The mean diameter of the nanoparticles was
23.48 nm, with the maximum diameter at 32.5 nm and the
minimum diameter at 13.75 nm ± 0.04.
For personal use only.

Figure 8 shows the transverse morphology of films de-

Fig. 7. FEG – SEM of sample E12.
Fig. 9. Power, Current and Voltage parameters used in depositions.
posited on internal samples, and Fig. 9 shows the average
thicknesses of films deposited according to the previous
figure. Figure 8a and b, samples E6 and E12 respectively,
shows the presence of continuous, dense film, the average
thicknesses were 8.24 ± 1.5 lm and 15.7 ± 0.36 lm respec-
tively for the samples E6 and E12. However, Fig. 8c and d
show that whilst the film seems to be continuous, it is actu-
ally composed of micrometric particles, suggesting that the
size of particles extracted from cathode walls when the
length-to-distance ratio is greater than 1,5 negatively im-
pacts adhesion to the substrate, the average thicknesses
were 8.86 ± 0.75 lm and 3.95 ± 0.78 lm, respectively for
the samples E18 and E24. As the same temperature was
used in all treatments, we can affirm that for length-to-dis-
tance ratios greater than 1.5, higher temperatures are
needed in order to promote dense film formation.
This factor may be related to the potential used in this
work. As illustrated in Fig. 9, the highest potential was
found in sample E12. When comparing potentials used in
samples E6, E18 and E24, we note that there is a direct rela-
tionship between plasma potential and deposition effi-
ciency, as sample E6 has a deposition potential equal to or
lower than that of samples E18 and E24. However, as the
current used was directly proportional to plasma ion den-
sity, and with increasing length-to-distance ratios resulting
in higher treatment currents, we can affirm that deposition
efficiency decreased because there was a reduction in the
treatment current, which signified lower electric field inten-
sity and consequent lower particle kinetic energy. This can
be related to Fernandes et al.’s [19] study because if parti-
cles extracted from cathodes are larger, more energy is
needed for movement and subsequent deposition on the
glass substrates.

5
 F. M. Fernandes et al.: Deposition of fine copper film on samples placed internally and externally to the cathodic cage
4. Conclusions
As a result of this work, we conclude the following:
-The thickness of the cathodic cage versus the hole dia-
meter ratio influence on the deposition of films, neverthe-
less, the use in metallic materials must be studied for pur-
pose of evaluation of the diffusion of elements in metal
matrices;
- These results lead us to believe that for internal deposi-
tion, the thicknesses of larger cages can reduce the time of
nitriding as well as the temperature;
- The cathodic cage technique demonstrated potential for
the deposition of nanoparticles of metallic materials, how-
ever, for external deposition process it is necessary to con-
sider the sample temperature and the adhesion of the film
International Journal of Materials Research downloaded from www.hanser-elibrary.com by Hanser - Library on January 28, 2019
to the substrate for future studies;
- The highest fine copper film deposition efficiency was
obtained using a length-to-distance ratio of 1.5;
- On samples placed externally to and distant from the
cathodic cage, and exposed to lower temperatures, only
copper nanoparticle deposition occurred, as opposed to the
formation of dense film;
- With length-to-distance ratios higher than 1.5 requiring
more current, there is a drop in plasma potential resulting in
lower kinetic energy particles.
We thank the Departamento de Materiais – DEMat Laboratory, and
Materiais Multifuncionais e Experimentação Numérica da Escola de
For personal use only.
Ciências e Tecnologia – ECT of the Universidade Federal do Rio
Grande do Norte – UFRN Lab.
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Correspondence address
Ph. D. Thércio Henrique de Carvalho Costa in Materials Science and
Engineering
Mechanical engineering department
Federal University of Rio Grande do Norte, Natal-RN, Brazil
Avenue Senador Salgado Filho – Lagoa Nova
Natal/RN – 59078-970
Brazil
Tel: +55 84 33422233
E-mail: thercioc@ufrn.edu.br
Orcid: 0000-0001-7429-4273
Web: http://lattes.cnpq.br/3647710047561421
Bibliography
DOI 10.3139/146.111737
Int. J. Mater. Res. (formerly Z. Metallkd.)
110 (2019) E; page 1 – 6
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