coatings
Article
Chemical Stability of Sputter Deposited Silver Thin Films
Diederik Depla
Citation: Depla, D. Chemical
Stability of Sputter Deposited Silver
Thin Films. Coatings 2022, 12, 1915.
https://doi.org/10.3390/
coatings12121915
Academic Editor: Torsten Brezesinski
Received: 10 November 2022
Accepted: 3 December 2022
Published: 7 December 2022
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Coatings 2022, 12, 1915. https://doi.org/10.3390/coatings12121915
Department of Solid State Sciences, Ghent University, Krijgslaan 281 (S1), 9000 Gent, Belgium;
diederik.depla@ugent.be; Tel.: +32-9264-43-32
Abstract: Silver films with a thickness below 50 nanometer were deposited on glass using DC
magnetron sputtering. The chemical stability of the films was investigated by exposure of the film to
a droplet of a HCl solution in a humid atmosphere. The affected area was monitored with a digital
microscope. The affected area increases approximately linearly with time which points to a diffusive
mechanism. The slope of the area versus time plot, or the diffusivity, was measured as a function of
the acid concentration, the presence of an aluminum seed layer, and film thickness. The diffusivity
scales linearly with the acid concentration. It is shown that the diffusivity for Al-seeded Ag films is
much lower. The behavior as function of the film thickness is more complex as it shows a maximum.
Keywords: silver thin film; sputter deposition; chemical stability; diffusivity
1. Introduction
Thin silver films are used in a wide range of applications including antibacterial
coatings [1] and different optical devices [2]. Silver thin films are deposited on a large scale
as low emissivity (low-E) multilayers to improve the insulating properties of glazings [3,4].
Another application field of this type of multilayers is as transparent anode materials
with low sheet resistance and high transparency which could replace the more expensive
indium-based materials [5,6]. The multilayers consist of a stack of a metal layer sandwiched
between two dielectric layers, such as aluminum-doped zinc oxide or TiO2 [7,8]. The three
layer structure is often repeated, and one refers to the number of repetitions as a single,
double, or triple low-E coating [9]. The multilayer acts as an optical filter to control the
heat flux through architectural glazings. The filter must combine a high visual with a
low infra-red transmittance. The optical properties of silver makes it the preferred metal
used in low-E coatings. The fabrication of a thin silver film is challenging due its inherent
three-dimensional growth on weakly-interacting substrates, such as most oxide films
used in low-E coatings. Due to the tendency for 3D growth, continuous films can only
be obtained at a relatively high mean film thicknesses. Therefore, strategies have been
developed to overcome this problem. Silver can be alloyed with other elements [10–14].
Additionally, the use of gaseous surfactants has been reported [12,15,16]. The most common
approach is however the deposition of metal seed layers prior to the silver deposition.
The seed layer is typically a non-continuous thin film which affects the silver film growth.
Prior to the deposition of the covering dielectric film, another often non-continuous layer,
known as a blocking layer, protects the silver from reactive process conditions during the
dielectric deposition. The optical properties of the low-E coatings are further optimized by
material combinations, film thicknesses, and deposition conditions. The latter is currently
performed in-line on large area coaters by magnetron sputtering [8,17]. The choice for the
latter technique is mainly motivated by the good scalability of technique and the accurate
control of the deposition rate.
Silver based low-E multilayers are vulnerable to humid air [18–24]. Therefore, the
multilayer is deposited on the interior of the double glazing. Double glazings will normally
fail due to internal fogging, when moisture appears between the panes. With an anticipated
20 year lifetime of double glazing, the long term chemical stability of silver thin film is
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Coatings 2022, 12, 1915 2 of 14

an important feature. The protection of the multilayer in this way is however not always
possible for the aforementioned applications.
Hence, the degradation mechanism of silver based low-E multilayers has been investi-
gated in detail [19]. The proposed degradation model is based on a post-exposure study
of degradation spots formed on ZnO/Ag/ZnO multilayers and Ag thin films exposed to
a 95% relative humidity at room temperature over a saturated KCl solution. The spots
contain a central particle which seems to act as an entry point of water, or result in a thinner
film close to the particle due to geometrical shadowing effects during deposition. The
degradation spot consists of agglomerated silver around the central particle. In the case
of coated Ag layers, this agglomeration results in mechanical stress in the top dielectric,
which can lead to delamination of the layer. Similar spots are observed during salt spray
test on low-E coatings [14] or long-term exposure to high humidity conditions [25]. The
role of the air humidity on the formation of “corrosion spots” has also been reported for
other ultra-thin metal layers used in magnetic devices [26].
The origin of the silver agglomeration is less highlighted in the proposed degradation
model [19]. A comparison with silver agglomeration due the thermal annealing is made
with the minimization of internal and surface free energy and the important role of the
surface diffusivity of Ag atoms as the driving force. The comparison seems to be plausible.
Indeed, the agglomeration kinetics is based on hole growth [27] which can have multiple
causes, such as grain boundary grooving, in the case of thermal annealing. As grain
boundaries are more vulnerable to chemical attacks, grain boundary atoms will more easily
and rapidly dissolve than atoms within the grains. This selected attack when the silver layer
is exposed to humid air, could lead to holes exposing the substrate which will be followed
by hole growth and an agglomerated silver film as a final result. This proposed mechanism
agrees with the observations of Ross [19] as a chemical analysis of the islands uncovers no
other elements than silver. Moreover, as silver is known to have a high surface diffusivity
[28] it can be expected that especially thin silver films are quite sensitive to degradation
through this mechanism as hole growth depends strongly on surface diffusion [29]. The
silver aggregation can be further triggered by the interaction with chlorine atoms [30,31].
Although quite some knowledge has been gathered on the chemical stability of low-E
coatings, and silver thin films in general, the kinetics of the degradation spot formation
is, to the best of my knowledge, not studied in detail. In this study, the spot formation is
induced on sputter deposited silver films by a local exposure to a diluted HCl droplet. The
kinetics of the process is followed in situ. Image analysis permits a quantitative analysis of
the spot size as function of the HCl concentration, film thickness and the presence of an
aluminum seed layer.

2. Materials and Methods

A custom-made setup was built to follow the degradation spot formation (Figure 1).
The sample is placed on a transparent glass plate. The glass plate is supported by the water
cup. The water cup is a torus which can hold a tube. Distilled water is present between
the tube interior and center of the water cup. The water cup is closed at the bottom by a
transparent glass cover. The top of the tube is closed with a similar cover. As such, no water
can evaporate and the humidity inside the tube will be close to 100%. A digital microscope
(Dino-Lite, AM4115TL, 1.3 Megapixel) is placed on top of the upper glass cover. The opaque
microscope support prevents light from entering from the top. The internal light source of
the microscope is switched off. A bright white LED light source is placed below the set-up
(not shown). The light source was cooled with a fan. The measuring procedure starts by
placing the sample on the sample plate. A small alumina ring (diameter 2.75 mm, height
2 mm) is placed on the sample. The alumina ring ensures an equal contact area. Preliminary
experiments showed that the droplet shape can change during the experiment and/or be
different for films deposited under different conditions. A 3 µL droplet of diluted HCl
solution is injected in the ring with a pipette. The tube is placed over the sample, and
closed with the top glass cover and the microscope.
Coatings 2022, 12, 1915 3 of 14

Prior to the measurement, the digital microscope settings are tuned to have an optimal
image. After optimization, the auto-exposure setting was switched off together with the
auto-white balance option. A constant exposure of the sample is necessary for further image
analysis. Images at a 10-fold magnification were recorded at a fixed time interval using
the camera software. The area of the degraded region was measured using ImageJ [32].
Calibration was performed using size of the alumina ring (approximately 120 pixels/mm).
The blue channel of the image was converted into a binary image which can be automatically
processed using the Analyze particles function of the ImageJ software.

Digital microscope

Microscope support

Transparent glass cover

Tube
Sample plate

Water cup

Transparent glass cover

position light source

Figure 1. Set-up to measure the degradation spot formation. The tube is cut open to show the set-up
interior and the sample holder. The light source (not shown) is cooled with a ventilator (not shown)
to avoid heating and water condensation.

Silver thin films were deposited on glass substrates that have been ultrasonic cleaned
in a mixture of distilled water and ethanol (70% ethanol/30% water). The higher content of
alcohol allows a faster drying of the substrates. A high vacuum chamber was pumped by
a combination of a turbomolecular pump and a rotary pump. The base pressure during
film deposition was lower than 4 × 10−4 Pa, as measured with a Penning pressure gauge.
The argon pressure (0.5 Pa measured with a capacitance pressure gauge) was set by the
introduction of argon at a rate of 36.8 standard cubic centimeter per minute (sccm) using
a mass flow controller (MKS Instruments, Andover, MA, USA). A silver target (2 inch
in diameter, 6 mm thick) was placed on a planar cylindrical magnetron powered by a
Hüttinger 1500 DC power supply. The discharge current was fixed at 0.06 A which results in
a discharge voltage of 369 V. The target-substrate distance equaled 10 cm. Another, identical
magnetron, holding an aluminum target (3 mm thick), was placed directly opposite the
silver magnetron. The target–substrate distance was 12 cm. The aluminum magnetron was
used to deposit silver thin films with an aluminum seeding layer. First, the seed layer was
deposited at the aforementioned pressure and discharge current. After sputter cleaning
the silver target to avoid cross-contamination, the sample holder was flipped to expose the
sample to the silver magnetron.
In the case of silver, the deposition rate was calculated from the deposition time and
the film thickness as measured with X-ray reflectivity. At the aforementioned conditions,
the deposition rate equals 0.340 ± 0.034 nm/s. In the case of aluminum, several thicker
layers were deposited, and their thickness was measured with a stylus profilometer (Taylor
Hobson, Talystep, Leicester, UK). The deposition rate was calculated based on the deposi-
tion time and the measured thickness. Based on this calibration the film thickness of the
Coatings 2022, 12, 1915 4 of 14

seed layer is approximately 0.5 nm (15 s deposition time at 0.06 A, and 306 V, at 0.5 Pa for a
target-to-substrate distance of 12 cm).
The film resistivity was measured using a four probe (in-line) Van der Pauw method [33].
The resistivity measurement was performed directly after the film deposition. The films
and the degradation spots were analyzed with by SEM-FEG (Fei Quanta, FEI, Hillsboro,
OR, USA). X-ray diffraction (XRD) measurements in Bragg–Brentano configuration were
performed with D8 Bruker (Billerica, MA, USA) set-up equipped with an Euler cradle.
X-ray reflectivity (XRR) measurements were performed on a similar set-up. XRR and XRD
measurements were performed on thin films deposited on RCA (Radio Corporation of
America) cleaned silicon. Atomic force microscopy (AFM) measurements were performed
on a Bruker Dimension Edge system.

3. Results
3.1. Image Analysis
Figure 2 shows a typical result of the degradation experiment. Figure 2a shows the
evolution of the degradation spot as function of time. The images are taken at an interval of
45 s. The dark ring in the center of each image is a small alumina cylinder which holds the
HCl solution droplet. The area of the affected region was measured (Figure 2c) using the
ImageJ analysis software. The area increases, after a short initial delay, linearly with time.
This points towards a diffusion-based mechanism. From the slope of a linear fit through the
data, the associated diffusivity can be calculated. Subtraction of the initial recording from
the other images permit the changes to be highlighted. Figure 2b shows the result for the
last image taken. The degradation spot appears to be composed of three concentric rings.

(a) (b) 160

(c)
(3) 120
(2)
area (mm )
2

80
(1)
2
40 D = 0.183 mm /s
2
r = 0.999682
0
10 mm 10 mm 0 200 400 600 800 1000
time (s)
Figure 2. The growth of the degradation spot. Experimental conditions: silver thickness is approxi-
mately 17 nm (50 s deposition). HCl concentration equals 0.5 wt%. (a) Images taken at an interval
of 45 s. (b) Difference between the last image and first image. The spot consists of three different
concentric rings: a large central ring (1), followed by a less broad ring (2), and a final ring which is at
the rim of the degradation spot (3). (c) The area of the degradation spot as function of time. The blue
line is a linear fit to the data. The slope of the line is D which equals in this case 0.183 mm2 /s.

3.2. Influence of HCl Concentration

A series of experiments was performed to investigate the influence of the HCl concen-
tration on the diffusivity. The silver mean film thickness was fixed at approximately 20 nm
(deposition time 60 s). For each concentration, a minimum of three films were deposited
and consecutively tested. Six concentrations were tested in a concentration range between
0.25 wt% and 2.5 wt%. The diffusivity increases linearly with the HCl concentration. The
slope equals 0.44656 mm2 .s−1 .wt%−1 . The line goes through the origin (r2 = 0.9942) which
indicates that at the timescale of the experiment (max. 10 min) the silver film is not affected
by the humid atmosphere when no HCl is present.
Coatings 2022, 12, 1915 5 of 14

3.3. Influence of Film Thickness

The influence of the silver film thickness on the diffusivity D was investigated by
exposing the layers to a fixed concentration of 0.5%wt HCl solution droplets (see Figure 3).
The error was calculated as the standard deviation of four deposition/exposure combina-
tions. Despite the large error for some individual thicknesses, it is clear that the diffusivity
increases initially with increasing thickness. At a film thickness of approximately 30 nm,
the diffusivity maximizes and then decreases with increasing thickness.
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Figure 3. Influence of the film thickness/deposition time on the diffusivity for silver thin films
deposited on glass without seed layer (red) and with an Al seed layer (blue). The green line is a
smoothed spline through the data points related to the growth rate of the corrosion spot. The ratio of
the resistivity, as measured ex situ using a Van der Pauw set-up, between film deposited with and
without seed layer is shown on the right hand axis (purple points and line (only to guide the eyes)).

3.4. Influence of the Seed Layer

The experiments discussed in previous section (Section 3.3) were repeated with a
aluminum seed layer. The nominal thickness of the aluminum layer was fixed at 0.5 nm.
The seed layer results in strong drop of diffusivity D. The diffusivity is significantly
different from non-seeded layers with similar thicknesses, except for the thinnest film
(deposition time 25 s, mean film thickness 8.5 nm). An ANOVA test shows that between
the four studied thicknesses for the seeded layers no significant differences exist. Hence,
there is no thickness dependency (blue markers Figure 3) and the average diffusivity equals
0.087 mm2 ·s−1 (± 0.030, 95% confidence interval).

3.5. Film Characterization

3.5.1. As-Deposited Films
Samples of both seeded and non-seeded as-deposited films were analyzed with differ-
ent techniques. The following paragraphs give an overview.
Seeded and non-seeded layers were analyzed using SEM. Seeded layers become
continuous at a smaller nominal thickness. For example, a thin film with a nominal
thickness of 6 nm without seed layer (image b, Figure 4) has a similar surface morphology
as a seeded layer with a nominal thickness of 3 nm (image c, Figure 4).
The influence of the seed layer on the film resistivity measurements can be interpreted
in the same way as above. It is possible to measure a film resistivity for seeded Ag films
with a thickness as small as 3.3 nm while for the films deposited without seed layer the first
measurement is only possible for a thickness of 4.4 nm. This indicates that the percolation
threshold is reached at smaller mean thicknesses for the seeded layers. A plot of the Rt2film
Coatings 2022, 12, 1915 6 of 14

vs. the film thickness, with R the film resistance and tfilm the film thickness (not shown),
has a minimum which have been connected the continuity threshold [34]. A value of
approximately 10 nm is obtained for Ag, while 6 nm is measured for Ag/Al thin films.
Further, it can be observed from Figure 3 (right axis) that the same film resistivity is only
measured at a film thickness at approximately 27 nm (80 s deposition).

a) b)

c) d)

500 nm

Figure 4. SEM top view of thin films deposited on silicon. Top images (a,b) show SEM top view
images of non-seeded Ag layers with a nominal thickness of 3 nm and 6 nm, respectively. Bottom
images (c,d) show SEM top view images of seeded Ag layers with the same nominal thickness as
(a,b). The Al seed layer has a nominal thickness of 0.5 nm.

Figure 5 gives an overview of the AFM analysis. The AFM roughness confirms the
aforementioned observations. The thinnest films are very rough, especially for the non-
seeded layer. After a strong drop, the roughness further (slightly) increases with increasing
film thickness.
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Figure 5. The height distribution for non-seeded Ag (red) and seeded Ag (blue) films as measured by
AFM within a region of 5 µm × 5 µm. The top right figure displays the RMS average roughness as
function of the mean film thickness. The images (top) are AFM height profiles within a 1 µm × 1 µm
region for non-seeded and seeded layers with a mean film thickness of 31 nm.
Coatings 2022, 12, 1915 7 of 14

As demonstrated by the shown AFM images, for the two thickest films, the opposite
is observed, i.e., the height density distribution of the seeded layers shows a stronger
contribution of higher regions. The AFM images also show that the surface features for the
non-seeded thin film are much larger as compared to the seed thin film.

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Figure 6. XRR patterns for silver film deposited on Si without (left) and with (right) Al seed layer.
The silver films were deposited for 30 s, 60 s, and 90 s, and the aluminum layer for 15 s. This results
in Ag films of approximately 10, 20, and 30 nm and a Al film of 0.5 nm. The color traces show the
experiments, while the black lines are simulated patterns using Motofit [35].

XRR measurements for Ag thin films deposited on silicon with and without seed layer
are shown in Figure 6. The patterns were analyzed with MotoFit [35] and could be properly
fitted with a 2 layer/substrate model Ag/SiO2 /silicon. The major difference between both
series is noticed for the thinnest film. The film without seed layer has a higher interfacial
roughness (1.5 nm) as compared to the layer with seed layer (0.8 nm), which results in a
clear attenuation of the Kiessig fringes.
XRD patterns shows only (111) and (200) Bragg reflections (Figure 7). No other peaks
are observed. The intensity ratio I111 /I200 is for all mean film thicknesses larger than for a
random textured film which indicates that all films have a [111] out-of-plane fiber texture.
The domain size increases with increasing film thickness. Similarly to the texture, no
differences are observed between silver layers with and without Al seed layer.
Optical transmittance spectra (not shown) indicate slightly more transparent seeded
silver layers, but above a mean thickness of approximately 20 nm (60 s of deposition)
no differences between both films can be observed. The thinnest films show the typical
plasmon appearance for discontinuous thin films [36].
Coatings 2022, 12, 1915 8 of 14

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Figure 7. (a). The ratio between the diffraction intensity of the (111) and (200) Bragg reflection as
function of the deposition time (or apparent film thickness). The grey line indicates the same ratio for
a random textured silver film. (b). The domain size as calculated from the integral breath of the (111)
Bragg reflection. The Al seed layer has a nominal thickness of 0.5 nm. All films were deposited and
analyzed three times.

3.5.2. Exposed Films

Figure 8 shows an overview of a SEM analysis of a corrosion spot for a non-seeded
thin film with a nominal thickness of approx. 30 nm (90 s deposition) which was exposed
to a 0.5 wt% HCl droplet. The analysis was performed in the aforementioned three rings
(Figure 2). In the central region, the silver is agglomerated with the substrate exposed. The
broader ring (position B) consists of agglomerated silver but the substrate is not yet visible.
The smaller outer ring (position C) shows no silver agglomeration but small hillocks. Spots
on seeded Ag layers showed the same features, and possible differences were difficult to
quantify with SEM and/or AFM.

A B C

A BC

5 mm 10 µm
Figure 8. SEM analysis of the corrosion spot (deposition time 90 s without seed layer exposed to
0.5 wt% HCl). The sample was studied using SEM at the center of the colored circles, labeled A, B
and C, indicated on the digital microscope image shown at the left.

4. Discussion
The growth of silver thin films on weakly-interacting substrates, such as glass or
oxide covered silicon, has been reported in literature by many research teams. A good
overview permits our results to be benchmarked against literature. The growth starts
with the formation of nuclei or islands which grow until a connected network is formed.
The formation of the connected network is characterized by a strong drop in the electrical
resistivity, also known as the percolation threshold. An area filling factor of approximately
70% has been reported [37]. The holes in the network are further filled until a continu-
ous thin film is formed. The continuity threshold can be determined from the tensile to
compressive change of the incremental stress measured in situ during film growth [38].
Coatings 2022, 12, 1915 9 of 14

Alternatively, as mentioned before, the continuity threshold can also be determined from
the resistance(R)/film thickness (tfilm ) measurement as the on-set for film continuity is
connected with the minimum in the Rt2film data versus the film thickness. The mean film
thickness at the percolation and continuity threshold is mainly function of the substrate,
deposition technique, substrate temperature, and deposition rate. An overview is shown
in Figure 9. The percolation and continuity threshold for the films reported here are in
agreement with the reported literature trends (see violet closed and open markers for
non-seeded and seeded film, respectively).

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Figure 9. Reported percolation (hourglass symbols) and continuity (round) thresholds for silver
thin films deposited at room temperature using different techniques. Red symbols are for energetic
techniques (mainly sputtering), while blue symbols are for evaporation and e-beam experiments.
Green markers are for seeded layers. The seed material is mentioned in the reference list. The full
(striped) blue and red lines are fitted (calculated) power laws with an exponent −1/7 (see text). The
orange and purple lines are reproduced from the work of Jamnig et al. for films deposited at 40 and
52 ◦ C, respectively. The violet markers are used for this work (full and open marker for non-seeded
and seeded layer, respectively). Data taken from: (1) [39], (2(Ge)) [40], (3) [41], (4(Cu))[42], (5) [43],
(6) [44], (7) [45], (8) [46], (9) [47], (10) [48], (11) [49], (12) [50], (13) [51], (14) [52], (15) [53], (16) [54],
(17) [55], (18) [56], [19(ZnO)] [57], (20) [58], (21(CuO)) [59], (22) [60], and (23) [61].

From the compilation of these data, some interesting trends can be observed. Accord-
ing to Jamnig et al. [48] the influence of the deposition rate on the percolation and continuity
threshold for sputter deposited thin films at room temperature follows a power law with
an exponent of −1/7. The compilation for energetic deposition (red makers) confirms
this trend. The ratio between the percolation and continuity threshold is approximately
1.9 ± 0.2. The value agrees well with the expected value (1.75) based on 2D percolation and
a hole-filling mechanism of the formed network [62]. A similar trend can be extracted for
the percolation threshold for non-energetic (thermal and e-beam evaporation) deposition
(blue markers). The trend for the continuity threshold for these deposition techniques is
less clear.
Based on the fitted result for the energetic deposition, and the assumption that the
ratio between both thresholds is identical for both deposition strategies, the trend for the
continuity threshold can be calculated (see striped blue line, Figure 9). Most data agree
quite well with this trend. Additionally, two of the studies for sputtered silver films can be
connected to this trend (see data points (7) [45] and two data points of the (9) series [47]).
These experiments were performed at high deposition pressure which results in a low
Coatings 2022, 12, 1915 10 of 14

energy for the deposited atoms, similarly as for evaporation. One study (data series (3) [41]
on Figure 9) strongly deviates from the calculated trend. A possible explanation is that the
temperature control during these experiments was not successful and the experiments were
performed at an actually higher temperature than intended. Indeed, the data fit better with
the measured trends of Jamnig et al. [48] at higher deposition temperature (see purple line).
Another trend which can be observed from the complied data is the lower threshold values
for energetic deposition. This can be understood from ballistic effects, such as the break-up
of smaller islands or the formation of surface defects, which increase the nucleation density.
The study labeled as (23) [61] in Figure 9 is also interesting to mention as it compares
the growth of silver layers on borosilicate glass covered with different types of oxides. It
demonstrates that the percolation threshold depends on the substrate conditions as also
demonstrated by others [63]. From the compilation it is clear that seeded layers results
in a strong reduction in both thresholds. The presence of a seed layer results in a higher
nucleation density, and, hence, the silver layer becomes continuous at smaller mean film
thicknesses. Although this is the general trend, exceptions seem to exist. An evaluation of
several seed layers showed that Ta and Cr seed layers had the reverse effect, i.e., a higher
percolation threshold [64]. The same study showed that a thick seed layer (>0.1 nm) of Ni,
Mo, and Zr resulted also resulted in a higher percolation threshold. The usage of a seed
layer results according to most studies [65–69] in a smoother thin film.
The area of the corrosion spot linearly increases with time, which is characteristic
for a diffusive behavior. This is in agreement with studies of the wetting behavior of
droplets [70]. A very thin film of the order of 1 µm to 1 nm in thickness, known as the
precursor film,
q spreads ahead of the central cap droplet. The length of the precursor
increases as D f t, with D f a diffusion coefficient for the precursor, which agrees with
the observations made in this study. To avoid a macroscopic change of the drop shape,
and hence the results of the developed stability test, an alumina ring, which served as a
“cup” for the droplet, was used in this study. In this way, the liquid spreading is limited
to the precursor layer. According to hydrodynamic theory, the diffusion coefficient D f
equals H/3πηhliq with H the Hamaker constant, η the viscosity of the liquid, and hliq
the thickness of the precursor layer [71,72]. The Hamaker constant for Ag/H2 O has been
reported in a range between 30 and 400 × 10−21 J [73]. The viscosity of water at room
temperature equals 1 mPa.s. Literature on the precursor layer thickness for water is hard to
find. Studies on the adsorption of noble metals show that at high humidity the adsorption
layer is a few monolayers thick, or in the order of a few nanometer [74,75]. Using the
aforementioned values, diffusion coefficient equals to 0.01 to 0.13 mm2 ·s−1 . The diffusion
coefficients reported in this paper fit in this wide range. However, most of the studies have
been performed for the spreading of Van der Waals liquid droplets under “dry” conditions,
while, in this study, the spreading is performed under humid conditions. Moreover, as the
silver thin film interacts with the acidic liquid, the behavior is probably more complicated.
Indeed, the HCl concentrations are too low to strongly affect the water properties which
define the liquid spreading. The diffusion coefficient depends however strongly on the
HCl concentration. Hence, one can expect an interaction between the formation of the
discontinuous layer and the liquid spreading. Nevertheless, studies on reactive wetting
show similar behavior as reported here [76]. Additionally, the wetting behavior of the
precursor layer can be influenced by the surface roughness. The behavior has only been
described in the micron range [70]. According to the same study, the diffusion coefficient
for the precursor layer scales with the roughness amplitude, and, hence, it can be expected
that the foot spreads faster on a rough surface. This could explain the difference between
the seeded and non-seeded films but the initial increasing growth rate of the affected area
with increasing thickness for the non-seeded layers seems to conflict with this reasoning
as the roughness initially decreases with film thickness. Further, the difference in RMS
roughness between the two series is relatively small while the value for the diffusivity for
the non-seeded layers is on average 3 times larger as compared to the seeded layers.
Coatings 2022, 12, 1915 11 of 14

As mentioned in the Introduction, the dewetting of the silver layer or its conversion
from a continuous layer to an agglomerated microstructure can be understood from the
chemical attack of the grain boundaries which leads to the formation of hole which are
unstable. Both seeded and non-seeded films have a similar crystallite size (see XRD results)
which excludes a difference in grain boundary density as a possible explanation for the
observed difference in stability. When the hole growth is controlled by surface diffusion, the
growth rate is proportional with 1/h3 with h the film thickness [27,29]. Hence, thicker films
are more stable. For the thinnest films, the seeded films contain fewer regions with lower
thickness which enhances their stability (see AFM results). Nevertheless, the increasing
diffusivity as function of the mean film thickness for non-seeded layers seems to oppose
the above reasoning. Moreover, the non-seeded films with a thickness in the range of the
maximum observed diffusivity have a similar roughness, height density distribution as the
seeded layers. Further also the other studied properties, such as film resistivity, texture,
and domain size, do not significantly differ between both series for these film thicknesses.
One possible reason for the influence of the seed layer can be a difference in the surface
diffusivity of silver as the latter property affects the hole growth. It is fair to compare the
surface diffusion rate under the given conditions with surface diffusion rates reported for
silver in vacuo as the diffusion rate for Ag is hardly affected by the presence of water [77].
It has been reported that the activation energy for surface diffusion is much higher for
Ag on other metal surfaces [78]. The latter study provides no information of the Al/Ag
combination but a higher activation barrier for Ag on Cu is reported. Additionally, for
layers seeded with Cu, an improved chemical stability has been reported[42]. As discussed
in the introduction, another strategy to improve the stability of the silver layer is alloying.
It is interesting to remark that also a lower surface diffusivity was used to explain the lower
roughness of Al-doped Ag thin films [11], and that the addition of Cu to Ag reduces the
surface diffusivity [79].
Another possible reason which can explain this difference in diffusivity is the intrinsic
film stress. Using the same mechanism for agglomeration, Srolovitz and Goldinder [27]
reason that presence of a stress of either sign within the film decreases the film stability. As
the stored elastic energy density increases with increasing film thickness, the dewetting
mechanism will be enhanced as the energy release will be an additional driving force. A
similar reasoning was presented for epitaxial silver films deposited on silicon [80]. The
increased film thickness, however, will also stabilize the film as discussed before. This could
explain the observed maximum in the diffusivity for the non-seeded layers. A difference
between germanium seeded and non-seeded silver layers regarding the stress evolution
has been reported [81]. The final stress state, i.e., after relaxation of the incremental stress,
was function of the lateral size of the surface features as measured with AFM (defined as
the grain size in that study [81]) and the deposition rate. Increasing the deposition rate
results in more compressive films, while larger surface features results in a more tensile
films. Therefore, the difference in AFM surface features observed between non-seeded
and seeded thin films (Figure 5) could result in a difference in the stress state which can
influence the chemical dewetting behavior.

5. Conclusions
This study focuses on the chemical stability of seeded and non-seeded thin silver
films. Silver films agglomerate under the influence of the chemical attack. Therefore, the
stability was studied by measuring the growth rate of the agglomeration region. The area
of the agglomerated region increases linearly with time. The difference in stability between
non-seeded and seeded layers is not yet fully elucidated. Possible mechanisms are based
on a difference in the surface diffusivity of silver and/or the stress state. Further research
on the role of the material dependency of the seed layer and stress are, therefore, required
to further unravel the details of the proposed mechanism.
Coatings 2022, 12, 1915 12 of 14

Funding: This research received no external funding.

Data Availability Statement: All data can be obtained by a simple request to the author.
Conflicts of Interest: The author declares no conflict of interest.

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