Vacuum 137 (2017) 1e7

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Vacuum
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Structural and Morphological study of ZnO-Ag thin films synthesized

by reactive magnetron co-sputtering
R. Francq a, b, R. Snyders a, b, **, P.-A. Cormier b, *
a
Materia Nova Research Center, Avenue Copernic 1, Mons, Belgium
b
Chimie des Interactions Plasma-Surface, CIRMAP, University of Mons, Place du parc 20, Mons, Belgium

a r t i c l e i n f o a b s t r a c t

Article history: Zinc oxide (ZnO) is well-known to present, among other properties, a good antibacterial activity which
Received 7 July 2016 could be enhanced by the addition of Ag. The efficiency of ZnO-Ag films is correlated to the Ag con-
Received in revised form centration which should not exceed a threshold of a few atomic percent. Therefore it is necessary to
19 October 2016
develop a synthesis method allowing a perfect control of the film properties which can be easily
Accepted 21 October 2016
Available online 24 October 2016
transferred to the industry. In this context, we have developed a reactive magnetron co-sputtering
process, in which, a Zn and an Ag metallic targets are co-sputtered in Ar-O2 gas mixtures. ZnO-Ag thin
films were successfully grown, in which the Ag concentration can be tuned with a precision of 0.2%. The
experimental data reveal that the incorporation of Ag disturbs the ZnO crystalline structure, and that Ag
migrates to the film surface and agglomerates as a function of time for at.%Ag > 1.5%. The latter phe-
nomenon takes place several days after the film synthesis when they are stored under ambient condi-
tions, and is associated to oxydo-reduction reactions between oxygen and silver atoms.
© 2016 Published by Elsevier Ltd.

1. Introduction between oxygen species ($O 2 , $OH, H2O2) created by light ab-
sorption, and the cell proteins and membrane [13]e[15]. It is well
Zinc oxide (ZnO) is a well-known material which possesses accepted that the photocatalytic properties of an oxide can be
several interesting properties such as a high photoactivity, a n-type enhanced by doping the material with a transition metal. In this
conductivity and transparency in the visible range [1] … It is also a way, several metals were used as dopant such as La, Cu, Ta, Sn, Au
non-toxic and a low cost material. Altogether, these properties and Ag, showing an improvement of the photocatalytic activity
make ZnO suitable for a large variety of industrial applications, such [16]e[22]. Besides the good photocatalytic properties, the addition
as gas sensors [2], piezoelectric devices [3], photocatalysts [4], solar of Ag in ZnO matrices leads to the improvement of the antibacterial
cells [5] [6], and surface acoustic wave (SAW) devices [7]. ZnO has activity [13], [23]. Indeed, both Zn2þ and Agþ ions can electrostat-
also proved its usefulness as antimicrobial agent, inhibiting both ically react with the negatively charged cell membrane and cause
Gram-positive and Gram-negative bacteria [8]e[11]. The origin of the cell death [14].
the antibacterial activity of ZnO is not clearly understood and two ZnO-Ag is usually synthesized as a nanocomposite and has
mechanisms are generally invoked. The first one is described as already been generated by several techniques such as co-
follow: (i) the dissociation of ZnO molecules under aqueous con- precipitation [13] [14], [23], solvothermal [23], photochemical [4]
ditions, (ii) the generation of Zn2þ ions and (iii) the diffusion of the or pulsed laser deposition [24]. Three key parameters are re-
latter that accumulate within the cell leading to the rupture of its ported to influence the antibacterial properties of the films and
walls and the leakage of its content [11], [12]. The second mecha- have to be controlled: (i) the concentration of Ag, (ii) the dispersion
nism leading to the death of the bacteria is related to the reaction of Ag and (iii) the microstructure of the material. Indeed, as
mentioned by Zheng et al. [23], Ag nanoparticles should be ho-
mogeneously dispersed in the ZnO matrix to enhance the photo-
* Corresponding author. Materia Nova Research Center, Avenue Copernic 1, Mons, catalytic activity which is supposed to be the origin of the
Belgium. antibacterial properties. Nevertheless, the control of the dispersion
** Corresponding author. is challenging in view of the high tendency of Ag atoms to
E-mail addresses: [email protected] (R. Francq), rony.snyders@ agglomerate [25], [26]. Moreover, it is reported that the Ag content
umons.ac.be (R. Snyders), [email protected] (P.-A. Cormier).

http://dx.doi.org/10.1016/j.vacuum.2016.10.024
0042-207X/© 2016 Published by Elsevier Ltd.
2 R. Francq et al. / Vacuum 137 (2017) 1e7

should be less than 6% at. to ensure a good bactericide effect [9] controlled by the deposition time and confirmed by profilometry
[10], [14]. Finally, it is obvious that the morphology of the mate- (Dektak 150 profilometer). The elemental composition was deter-
rial will determine the effective surface area, i.e. the surface of mined by Electron Dispersive X-Ray (EDX). These measurements
interaction between ZnO-Ag and bacteria. were performed with a Hitachi SU8020 device using an accelera-
It is accepted that magnetron sputtering technique, which is tion voltage of 20 kV. The morphology of the films was observed by
widely used in the coating industry, allows a good control of the Scanning Electron Microscopy (SEM) using the same apparatus. The
morphology and the chemical composition of the film [27], [28]. crystalline structure was determined by X-Ray Diffraction (XRD)
Moreover, it allows the film deposition on complex substrates such technique in qe2q configuration using a PANalytical Empyrean
as powders [29]e[31] which could be very efficient to enhance the system (CuKa1,2 radiation). Depth profiles concentration were
effective surface area of the material. Therefore, this technique performed by X-Ray Photoelectron Spectroscopy (XPS) using a Phi
seems to be a promising approach for the growth of ZnO:Ag thin Versa Probe 5000 with an Al Ka (E ¼ 1486.7 eV) monochromatic X-
films for antibacterial applications [32]e[34]. Ray source. Depth profiles were performed by using an Arþ ions
In this work, aiming to control the film microstructure, the gun with a sputtering rate of 5 nm/min (estimated on SiO2).
concentration and the dispersion of Ag nanoparticles in ZnO, Zn
and Ag targets were reactively co-sputtered in Ar-O2 atmosphere. A
fine tuning of the Ag content in the ZnO film is shown as well as the 3. Results and discussion
effect of its concentration on the crystalline structure and the
morphology of the film. Finally, the mechanisms leading to the 3.1. Reactive sputtering of Zn
observed migration of silver at the surface of ZnO films were
studied. When considering reactive magnetron sputtering, it is well-
known that the introduction of a reactive gas such as O2 leads to
a modification of the target chemical state, i.e. the poisoning of the
2. Experimental details
metallic target surface. The latter induces nonlinear variations in
deposition parameters such as the target voltage, the deposition
All experiments were carried out in a cylindrical stainless steel
rate and the composition of the deposited thin film [27]. This is
chamber (height: 275 mm, diameter: 400 mm). The deposition
observed on Fig. 2 which shows the evolution of the target voltage
chamber was evacuated using a turbo molecular pump (EDWARDS
(UZn) recorded for 5 values of PZn. For low oxygen flows (2<FO2 < 5
nEXT300D) backed by a primary pump (Adixen Pascal 2015SD by
sccm depending on PZn), UZn is almost constant which is charac-
Pfeiffer Vacuum) to an ultimate pressure of 106 Torr. The system
teristic of the metallic mode. For these conditions, the flow of
was equipped with two K.J. Lesker Torus magnetron cathodes. A Zn
reactive gas is not high enough to allow a complete coverage of the
(2 in. in diameter and 0.25-in. thick) and an Ag (1 in. in diameter
target by a compound layer and metallic atoms are essentially
and 0.125-in. thick) targets were sputtered in Ar-O2 gas mixture.
sputtered. Increasing further O2 leads to a drastic decrease of UZn
The Zn target was placed at a distance of 13 cm from the substrate,
which reaches a stable value for 5<FO2 < 9 sccm depending on PZn.
whereas the Ag one was placed at a distance of 8 cm. Both
This marked discontinuity is associated with the well reported
magnetron cathodes were symmetric and oriented towards the
transition towards the compound mode. Indeed, for these condi-
substrate, forming an angle of 45 with the substrate surface
tions, the target is covered by a compound (ZnOX) layer and most of
normal (Fig. 1). Both targets were sputtered in DC mode using two
the sputtered particles are oxidized molecules. The shift of the
Advanced Energy MDX500 power supplies. Ar gas was directly
transition to higher FO2 values when increasing PZn is associated
injected at the Ag target surface in order to prevent its poisoning,
with an increase of the sputtering yield. Since the erosion rate of
while the oxygen flow was focused toward the Zn target. Silicon
the target surface is increased, a higher amount of oxygen is needed
wafers (100) or soda lime glass were used as substrates and rotated
to fully oxidize the latter.
at a speed of 5 rpm during the deposition procedure. The substrates
As expected, the deposition rate is influenced by the increase of
were cleaned with detergent (RBS) solution and rinsed with ultra-
PZn and presents a highest value for PZn ¼ 150 W (results not
pure water before deposition. Two stainless steel diaphragms with
an aperture of 6 and 12 mm in diameter, respectively, were alter-
natively placed in front of the silver target in order to limit the silver
content in the film. The total pressure (p) and the sputtering power
applied to the Zn target (PZn) were kept constant at 5 mTorr and
150 W, respectively. The power applied to the Ag target (PAg) ranged
from 7 W to 25 W. The total gas flow (Ar þ O2) was maintained
constant at 20 sccm.
All films present a thickness of 350 nm ± 25 nm, which was

Fig. 2. Zn target voltage (VD) as a function of the oxygen partial flow (O2%) for different
Fig. 1. Sketch of the experimental setup. PZn (p ¼ 5 mT, total gas flow: 20 sccm).
 R. Francq et al. / Vacuum 137 (2017) 1e7 3

shown). Based on these data, in order to grow stoichiometric ZnO depicts the deformation of the ZnO crystalline cell.
films as quickly as possible, PZn was fixed at the highest value
(150 W) and FO2 at 10 sccm. In these conditions, the ZnO film was 3.3. Effect of Ag on the microstructure of the ZnO films
crystallized and stoichiometric as it will be shown in the next parts.
The SEM planar (A) and cross-sectional (B) views of ZnO-Ag thin
3.2. Incorporation of silver in ZnO films films for an %Ag ranging from 0 to 6.5 ± 0.2 at% (numbered from I to
IV) are shown in Fig. 6. The films were synthesized at PZn ¼ 150 W
As mentioned in the introduction part, the control of Ag content using a pressure of 5 mTorr. The pure ZnO film exhibits a well
(%Ag) in the ZnO matrix is one of the key parameter determining oriented and dense columnar structure, which is consistent with
the antibacterial activity of the ZnO-Ag films. Most of the reports the zone 2 of the well-known structure diagrams reported by
relates that a content lower than 6 at.% is necessary [9] [10], [14]. Anders [35] and Thornton [36]. The addition of Ag in the ZnO film
Therefore, we have specifically studied this aspect of the material. induces an increase of the film porosity, keeping the columnar
In a first attempt, in addition to the reactive sputtering of Zn, PAg microstructure (samples II and III). The increase of the inter
was simply varied between 5 and 25 W. The films were charac- columnar space for these Ag contents (i.e. 0.4 ± 0.1 and 1.5 ± 0.2 at
terized by EDX and in these conditions, even by decreasing PAg %) could be explained by the incorporation of Ag particles between
down to 5 W, (minimum power required to ignite the Ag discharge) the columns. This can be clearly observed on the SEM images where
%Ag was still higher than 6% (Results not shown). Therefore, in the white points represent Ag aggregates appearing between and at
order to further limit the Ag particles flux arriving at the substrate the edges of the ZnO columns. This was verified by making a
surface, a stainless steel diaphragm was placed in front of the Ag composition contrast using back-scattered electrons (BSE) mode of
target. First, the aperture of the diaphragm was arbitrary fixed to the SEM apparatus (not shown). For higher %Ag, namely 4, 1 ± 0,2 at
12 mm in diameter. Using this aperture, the Ag content in ZnO films % and 6,5 ± 0,2 at.% (samples IV and V respectively), the
can be controlled between 2 and 8% by increasing PAg between 5 morphology of the film tends to be similar to the one of pure ZnO
and 15 W (Fig. 3). In order to extend our experimental window, a film. This could be explained by a different incorporation of Ag
second diaphragm of 6 mm in diameter was used to finely control % atoms into the ZnO matrix. Indeed, for these two samples, a thin
Ag between 0.3 ± 0.1 and 1.3 ± 0.2. layer of Ag is observed at the top surface of the film. For the sample
Another feature that has to be controlled is the crystalline IV, we can still distinguish the top of the ZnO columns below the Ag
constitution of the material. Fig. 4 shows the XRD patterns of ZnO- layer (inset in Fig. 6-IVA), whereas the columns are completely
Ag thin films prepared by reactive magnetron co-sputtering for covered for the sample V. As the SEM characterizations were per-
different %Ag: from pure ZnO to an Ag content of 8 at.%. According formed several hours after deposition, an ageing effect appearing
to the spectra, all films are only composed by the wurtzite ZnO only for high Ag content was suspected as the cause of this silver
phase (PDF00-035-1451), even when Ag is present (no Ag diffrac- accumulation.
tion peak). This is in accordance with the results of Wang et al. [32]
and could be explained by the too small size of the Ag nanoparticles 3.4. Ageing of the ZnO-Ag films
(AgNPs) that is less than 10 nm as shown on TEM image (Fig. 5).
Regardless the silver content, the films exhibit a preferred orien- To get a better insight in the mechanisms involved in the ageing
tation along the (002) direction, corresponding to the c-axis normal of the ZnO-Ag films, new films were deposited and the Ag con-
to the substrate. It is clear that the increase of the Ag content in the centration was followed during the ageing of the samples by per-
ZnO film leads to a decrease of the intensity of the (002) peak, forming XPS depth profiles. In order to get away from the surface
indicating a decrease of the ZnO cristallinity [32], [33]. This could be carbon contamination the Ag/Zn was considered. The depth evo-
explained by the substitution of Zn atoms by Ag ones, inducing lution of this ratio for low Ag containing films, 0.5 at % (PAg ¼ 10 W)
lattice defects [32]. This hypothesis is supported by the shift of the and 0,8 at % (PAg ¼ 15 W) respectively, is thus presented on Fig. 7.
(002) peak as it can be observed on the zoom shown on Fig. 4 which Both films exhibit a higher Ag/Zn ratio at the top surface than in the

10 1,8
a) Diaphragm 12 mm b) Diaphragm 6 mm
9 1,6
8
1,4
7
1,2
6
Ag (at. %)

Ag (at. %)

1
5
0,8
4
0,6
3
0,4
2

1 2 0,2 2
R =0.98
R =0.99

0 0
4 5 6 7 8 9 10 11 12 13 14 15 16 17 6 8 10 12 14 16 18 20 22 24 26
PAg (W) PAg (W)

Fig. 3. Silver content versus the power applied to the Ag target using two apertures of diaphragm: 12 (a) and 6 (b) mm, respectively. The experimental conditions were:
PZn ¼ 150 W, p ¼ 5 mTorr, FO2 ¼ FAr ¼ 10 sccm.
4 R. Francq et al. / Vacuum 137 (2017) 1e7

(102)

(103)
(002)

(110)
(100)
8%
5.6%
4.9%

(200)
3.2%
Intensity (a.u.)

(101)

1.2%
8%
5.6%
4.9%
3.2%
1.2%
(002)

ZnO
32 33 34 35 37 ZnO

25 30 35 40 45 50 55 60 65 70 75 80 85 90
o
2θ ( )
Fig. 4. XRDs patterns of ZnO-Ag films for various Ag concentrations (0e8 at.%).

higher Ag content: z 8 ± 0.3% (determined by EDX), just after

deposition, one week and one month after storage in ambient
conditions (J0, J7 and J35 on Fig. 8). Regardless the storage duration,
the Ag/Zn ratio decreases from the top surface to stabilize in the
bulk material at a value of z 0.1. At J0, the Ag/Zn ratio at the top
surface equals 0.55 and stabilizes after 10 nm in depth, demon-
strating that the migration and the agglomeration phenomenon
takes place just after the deposition. After 7 days of ambient con-
dition storage, Ag/Zn ¼ 34 at the film top surface (not visible on
Fig. 8 due to the y axis scale), and becomes null after 35 days,
meaning that only Ag is present at the top surface of the film.
Moreover, for J7 and J35 the stabilization of the Ag content in the
bulk occurs only after 20 nm, showing that a thin layer mainly
composed by Ag is formed. These results clearly demonstrate that
migration of silver occurred during the ageing of the film. Based on
these data, it appears that the high Ag content films (>0.8%) are
unstable and experience migration of Ag to the surface. The ten-
dency of the silver to migrate and agglomerate is a well-known
phenomenon that has already been reported in the literature for
several configurations of silver nanoparticles (AgNPs) such as in
low emissivity coatings [25] [37]e[39], waveguides [40], food
packaging [41] [42], or bare AgNPs [43], [44]. The migration and the
agglomeration of silver observed in our films could be explained by
Fig. 5. TEM image of ZnO-Ag film synthesized in the following experimental condi- successive oxidation and reduction of the AgNPs as described by
tions: PAg ¼ 10 W, PZn ¼ 150 W, diaphragm ¼ 12 mm, p ¼ 5mTorr. Glover et al. [44]. In fact, the AgNPs are oxidized by the oxygen and
the water coming from the ambient air, which leads to the release
of Ag ions. These ions can migrate through the thin layer of
bulk of the material. Nevertheless, it is clear that the migration and/
adsorbed water and agglomerate after reduction. As the ZnO-Ag
or agglomeration of Ag is limited since the Ag/Zn ratio differences
films are extremely porous, the water can reach AgNPs even if
between the surface and the bulk equal 0.04 and 0.01 for 15 and
they are located in depth. As mentioned by Liu et al. [43], the
10 W conditions, respectively. XPS profiles were also performed on
oxidation process by oxygen and protons from ambient air is a slow
a film synthesized with PAg ¼ 20 W, which should correspond to a
 R. Francq et al. / Vacuum 137 (2017) 1e7 5

Fig. 6. Planar views and cross section views (series A and B respectively) of pure ZnO (I) and ZnO-Ag thin films with an increasing silver content from view II to view V.
6 R. Francq et al. / Vacuum 137 (2017) 1e7

0,07 Finally, the reasons explaining the stability of low Ag containing

films are not totally clear, but might be related to the diameter or to
10 W
0,06 15 W the concentration of the AgNPs [45]e[47].

4. Conclusions
0,05

In this study, ZnOAg-containing thin films were prepared by

0,04 Reactive Magnetron Co-Sputtering varying the Ag concentration. A
Ag/Zn

protocol allowing a fine control of the Ag concentration in the ZnO

0,03 films, from 0,3 to 9 at.% was developed. The Ag content can be easily
tuned by modifying the deposition parameters. We have shown
0,02 that the Ag concentration influences both the crystallinity and the
microstructure of the ZnO films. The results show that below 2 at %
of Ag, the porosity of the film is enhanced compared to pure ZnO,
0,01
which indicates that the Ag atoms concentrate in the form of
nanoparticles between the columns. An increase of the Ag content
0 leads to the decrease of the film porosity and the accumulation of
0 5 10 15 20 25 30 35 40 45 50
Depth (nm) silver at the top surface. It was demonstrated by XPS depth profiling
that this accumulation is due to the migration of Ag particles
Fig. 7. At % Ag/At.% Zn ratio according to the depth of the film determined by XPS
through the ZnO films, likely along the columns. This migration and
profiling 3 weeks after deposition of ZnO-Ag films deposited with PAg ¼ 10 W (a) and
PAg ¼ 15 W (b). the agglomeration of silver that occurs at the top surface of the
films could be explained by successive oxidation and reduction of
the AgNPs. Future works will include the characterization of the
0.8 antibacterial activity of these ZnO-Ag thin films in view of
biomedical applications.
J0
0.7 J7
J 35 Acknowledgment
0.6
The authors acknowledge Sc. PhD Cristina Rojas Ruiz and Pro-
0.5 fessor Juan Carlos S

anchez Lo
pez from the Instituto de Ciencia de
Materiales de Sevilla (ICMS) for the TEM pictures. The authors are
Ag/Zn

0.4 also grateful to the Walloon Region for the financial support
through the ABBEADS First DoCA program.
0.3
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