Applied Surface Science 370 (2016) 306311

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Protection of brittle lm against cracking

J. Musil , J. Sklenka, R. Cerstv

y
Department of Physics and NTISEuropean Centre of Excellence, University of West Bohemia, Univerzitn 8, 306 14 Plzen,
Czech Republic

a r t i c l e

i n f o

Article history:
Received 11 November 2015
Received in revised form 8 February 2016
Accepted 13 February 2016
Available online 16 February 2016
Keywords:
Zr Si O lm
Mechanical properties
Transparency
Film cracking
Protective lm
Magnetron sputtering

a b s t r a c t
This article reports on the protection of the brittle Zr Si O lm against cracking in bending by the highly
elastic top lm (over-layer). In experiments the Zr Si O lms with different elemental composition and
structure were used. Both the brittle and highly elastic lms were prepared by magnetron sputtering
using a dual magnetron. The brittle lm easily cracks in bending. On the other hand, the highly elastic lm
exhibits enhanced resistance to cracking in bending. Main characteristic parameters of both the brittle
and highly elastic lms are given. Special attention is devoted to the effect of the structure (crystalline,
amorphous) of both the brittle and highly elastic top lm on the resistance of cracking of the brittle lm.
It was found that (1) both the X-ray amorphous and crystalline brittle lms easily crack in bending, (2)
the highly elastic lm can have either X-ray amorphous or crystalline structure and (3) both the X-ray
amorphous and crystalline, highly elastic top lms perfectly protect the brittle lms against cracking in
bending. The structure, mechanical properties and optical transparency of the brittle and highly elastic
sputtered Zr Si O lms are described in detail. At the end of this article, the principle of the lowtemperature formation of the highly elastic lms is also explained.
2016 Elsevier B.V. All rights reserved.

1. Introduction
It is well known that brittle lms very easily crack during bending when they are deposited on the exible substrates. The cracking
of the brittle lms is their serious drawback because the cracks created in the lm interrupt its function [112]. Therefore, it is vitally
important to prevent cracking of the brittle lms.
Recently, it was reported that the brittle lm can be protected against cracking by the elastic top lm (protective lm)
with the high hardness H 15 to 25 GPa, low elastic modulus
E* = E/(1 2 ) which results in a high ratio H/E* 0.1, high elastic
recovery We 60% and compressive macrostress ( < 0) [1316];
here E is the Youngs modulus and  is the Poissons ratio. In the
experiment described in Ref. [17] it was shown that the amorphous brittle lm over-coated by the crystalline elastic lm does
not cracks, i.e. the system of two layers brittle bottom lm/elastic
top protective lm exhibits an enhanced resistance to cracking.
However, there is a question if also the crystalline brittle lm can be
protected against cracking by an elastic top lm and if this elastic
top lm can also have the X-ray amorphous structure. The investigation of the effect of the structure of both the brittle lm and the

Corresponding author. Tel.: +420 377632201.

E-mail address: musil@kfy.zcu.cz (J. Musil).
http://dx.doi.org/10.1016/j.apsusc.2016.02.132
0169-4332/ 2016 Elsevier B.V. All rights reserved.

elastic protective lm on the resistance of cracking of the brittle

lm is the main subject of this article.
This article reports on the two-layer coatings composed of brittle bottom lm and top elastic lm with different compositions of
crystallographic structure of both lms: (a) a- + c-, (b) c- + c-, (c)
a- + a-, and (d) c- + a-; here a- and c- denotes the lm with amorphous and crystalline structure, respectively, see Fig. 1. Physical and
mechanical properties, and optical transparency of individual lms
(a- brittle, c- brittle, a- elastic and c- elastic) and couples of these
lms (the bottom brittle lm + the top elastic lm) are reported in
detail.
2. Experimental details
The Zr Si O coatings with different physical and mechanical
properties were deposited on the Si (1 0 0) substrate and the Mo
strip (60 10 0.1 mm3 ) by reactive magnetron sputtering using
a dual magnetron equipped with Zr/Si targets of 50 mm in diameter composed of a circular Si (1 0 0) plate ( 38 mm) xed to the
magnetron cathode by Zr xing ring with inner diameter in . The
dual magnetron was operated in ac pulsed bipolar mode generated by a pulsed power supply DORA MSS-10 with a maximum
output power 10 kW. The repetition frequency fr of pulses was
2 kHz and ac frequency of negative half-sinusoids inside pulses
was 112 kHz. More details on the deposition system are given in
Ref. [17].

J. Musil et al. / Applied Surface Science 370 (2016) 306311

307

Fig. 1. Four two-layer coatings composed of brittle bottom lm and top elastic lm with different combinations of the structure of bottom and top lms.
(a) crystalline/amorphous couple, (b) crystalline/crystalline couple, (c) amorphous/amorphous couple and (d) amorphous/crystalline couple.

The lms were sputtered under the following conditions: discharge current Ida = 1 A averaged over the pulse period T = 1/fr ,
target power density Sd = Pd /S 25 W/cm2 , substrate bias Us = U ,
the substrate temperature Ts = RT (the unheated substrate) and
500 C, substrate-to-target distance dst = 80 mm, partial pressure
of oxygen pO2 = 0 and 0.15 Pa for the brittle lms and the elastic lms, respectively, and total pressure pT = pAr + pO2 = 1 Pa;
here S is the whole area of the magnetron target and U is
the oating potential. At rst, single layer coatings were sputtered on the Si (1 0 0) substrate, glass substrate and the Mo strip
(60 10 0.1 mm3 ), their physical and mechanical properties were
measured and their resistance to cracking was assessed by bending of the coated Mo strip around a xed cylinder. Physical and
mechanical properties of sputter deposited single layer lms and
their elemental composition are given in Table 1. Then, two-layer
coatings with different crystallographic structure of the bottom and
top lms (layers) were sputtered. Their physical and mechanical
properties were also measured and their resistance to cracking was
also assessed by bending of the coated Mo strip, see Table 2. Both
lms in two-layer coatings were sputtered without an exposure to
the air simply by changing the partial pressure of oxygen pO2 in the
Ar + O2 sputtering gas mixture.
The structure of sputtered lms was characterized by X-ray
diffraction using an XRD diffractometer PANalytical Xpert PRO
in Bragg-Brentano conguration with CuK radiation. The elemental composition was determined by X-ray Fluorescence (XRF)
spectroscopy with PANalytical XRF Spectrometer MagiX PRO.
Mechanical properties of lms were determined from load vs.
displacement curves measured by a microhardness tester Fischerscope H100 with Vickers diamond indenter at a load L = 20 mN.
For all sputtered lms the ratio d/h of diamond depth impression
d in the lm and the lm thickness h was less than 0.1. It indicates

Fig. 2. X-ray (XRD) diffraction patterns of brittle amorphous (lm 1) and crystalline (lm 2) and elastic amorphous (lm 3) and crystalline (lm 4) Zr Si O
lms with properties summarized in Table 1.

that the measured hardness H of sputtered lms is not inuenced

by the substrate [18,19]. The macrostress  and the thickness h of
the lms were measured using a stylus prolometer DEKTAK 8. The
macrostress  was determined from the thickness h and curvature
of the lms deposited on Si (1 0 0) strips (35 5 0.64 mm3 ) using
a Stoneys formula [20]. The resistance of the lm to cracking was
tested by a bending test. The coating was deposited on a Mo strip
(80 10 0.1 mm3 ) and the coated Mo strip was bended around a
xed cylinder of diameter r up to the occurrence of cracks in the
coating surface. More details are given in Refs [1316]. The transparency of Zr Si O layers was measured in the range from 300 to
800 nm using a spectrometer Specord M400.
3. Results and discussion
3.1. Mechanical properties and structure of Zr Si O lms
Physical and mechanical properties of single-layer Zr Si O
lms are summarized in Table 1. From this table it is seen that
(1) the amorphous and crystalline lms can be (i) sputtered from
a composed Zr/Si target, see Fig. 2, and (ii) either brittle (easily crack) or highly elastic (resistant to cracking) lms can be
formed, (2) the brittle crystalline and amorphous lms exhibit a
low ratio H/E < 0.1, low elastic recovery We < 60% and tensile or
almost zero compressive macrostress ( = 0.3 GPa), respectively,

Table 1
Physical properties, elemental composition, mechanical properties, cracking and transparency T of single-layer Zr Si O lms used in experiments. Mechanical properties of
the lms deposited on Si (1 0 0) substrates were measured by micro-indentation at load L = 20 mN, the transparency T of the lms deposited on glass substrate was measured
at the wavelength  = 550 nm and the resistance to cracking of the lms deposited on Mo strip was characterized by the bending test.
Film No.

Structure

Behavior

h (nm)

aD (nm/min)

 (GPa)

Zr (at.%)

Si (at.%)

O (at.%)

H (GPa)

E* (GPa)

We (%)

H/E*

Cracking

T (%)

1
2
3
4

Amorphous
Crystalline
Amorphous
Crystalline

Brittle
Brittle
Elastic
Elastic

3300
3300
3300
3000

50
80
40
13

0.30
0.15
0.14
0.79

24
59
2
27

61
10
35
3

15
31
63
70

10.2
14.4
7.1
17.4

132
160
57
168

48
56
69
69

0.078
0.090
0.102
0.104

Yes
Yes
No
No

0
0
90
75

Table 2
Physical and mechanical properties, and cracking of two-layer Zr Si O coatings (bottom brittle lm, top elastic lm) on Si (1 0 0) substrates used in experiments. Mechanical
properties of the lm were measured by micro-indentation at load L = 20 mN, and its resistance to cracking was characterized by the bending of coated Mo strip.
Coating two lms

Structure

hb (nm)

ht (nm)

hT (nm)

Ts ( C)

 (GPa)

H (GPa)

E* (GPa)

We (%)

H/E*

Cracks in bending

1+4
2+4
1+3
2+3

a- + cc- + ca- + ac- + a-

3300
3300
3300
3300

3000
3000
3300
3300

6300
6300
6600
6600

RT/500
500/500
500/500
500/RT

1.1
1.3
0.2
0.35

17.1
17.3
6.1
6.3

160
159
57
60

68
66
63
61

0.107
0.109
0.107
0.105

No
No
No
No

Here hb is the thickness of the bottom lm (layer 1) and ht is the thickness of the top lm (layer 2).

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J. Musil et al. / Applied Surface Science 370 (2016) 306311

Fig. 3. Surface morphology of one-layer brittle lm (a) the amorphous lm (the

lm No. 1) and (b) the crystalline lm (the lm No. 2) after bending of coated Mo
strip (the lm/Mo strip couple) around cylinder of radius r = 10 mm. Physical and
mechanical properties of the lm 1 and 2 are given in Table 1.

(3) the elastic amorphous and crystalline lms resistant to cracking

exhibit a high ratio H/E* 0.1 and high elastic recovery We > 60%,
compressive macrostress ( < 0), high optical transparency in visible and IR regions and strongly differ in the content of Zr and Si, (4)
the elastic amorphous lm is soft and contains more Si compared
with Zr (Si/Zr > 1), (5) the elastic crystalline lm is hard and contains
more Zr compared with Si (Si/Zr < 0), (6) the brittle and elastic amorphous lms exhibit a low compressive macrostress ( < 0), (7) the
brittle crystalline lms exhibit tensile macrostress ( > 0) and low
hardness H 14 GPa, (8) the elastic crystalline lms exhibit a compressive macrostress ( < 0), relatively high hardness H 17 GPa
and almost the same value of the effective Youngs modulus E* as
the brittle crystalline lm. These properties are controlled by the
elemental composition of lms and their deposition rate aD , i.e. by
the energy delivered to the lm during its growth.
The combination of individual lms (layers) in the two-layer
Zr Si O coating makes it possible to nd the effect of the crystallographic structure and mechanical properties of the bottom and
top layer on its resistance to cracking in bending.
3.2. Resistance of two-layer coatings to cracking in bending
At rst, the brittle amorphous (the lm No. 1) and the brittle crystalline (the lm No. 2) lms, i.e. the single-layer Zr Si O
lms, deposited on Mo strip were bended around cylinder of
radius r = 10 mm. Both coatings cracked in bending due to low ratio
H/E* < 0.1 and low elastic recovery We < 60%, see Fig. 3 and Table 1.
Cracks are perpendicular to the direction of bending. On the other
hand, the elastic amorphous (the lm No. 3) and the elastic crystalline (the lm No. 4) single-layer lms deposited on Mo strip do
not crack and exhibit no cracks after bending around cylinder of
radius r = 10 mm due to high ratio H/E* > 0.1 and high elastic recovery We > 60%.
Then, both brittle lms (the lm Nos. 1 and 2) were overlapped
with the highly elastic top lms exhibiting high ratio H/E* 0.1,
high elastic recovery We > 60% and compressive macrostress ( < 0).
Four two-layer Zr Si O coatings composed of the brittle bottom
and the elastic top lm with different combinations of the lm

structure (a) a-/a- (lm No. 1/lm No. 4), (b) c-/c- (lm No. 2/lm
No. 4), (c) a-/a- (lm No. 1/lm No. 3) and (d) c-/a- (lm No. 2/lm
No. 3) were sputter deposited on the Mo strip. These two-layer
(brittle lm/elastic lm) Zr Si O coatings deposited on the Mo
strip were investigated against cracking. No cracks occurred in all
two-layer Zr Si O coating in which the brittle bottom lm was
covered by the elastic top lm after bending of the coated Mo strip
around cylinder of small radius r = 10 mm, see Fig. 4.
Here, it is worthwhile to note that both amorphous and crystalline lms can be either brittle or highly elastic. The brittle lms
are characterized by low values of the ratio H/E* < 0 and the elastic recovery We < 60%. On the other hand, highly elastic lms are
characterized by high values of H/E* 0 and the elastic recovery
We 60%. It means that different combinations of the amorphous
and crystalline brittle and elastic lms can be used (i) to prevent
cracking of the bottom brittle lm in bending and (ii) to create
advanced exible two-layer coatings with new unique properties.
For instance, the relatively soft X- ray amorphous Zr Si N lm
with low hardness H < 10 GPa, high ratio H/E* > 0.1 and compressive
macrostress ( < 0) can be also highly elastic and resistant to cracking, see the lm No. 3 in Table 1. What kind of the lm is formed, it
depends on the deposition conditions used in its formation, mainly
on (i) the energy delivered to lm during its growth, (ii) elemental
composition of lm and (iii) the melting temperature Tm of the lm
material. For more details see Refs. [1316].
Also, it is worthwhile to note that the brittle/elastic/brittle/
elastic multilayer lm can also exhibit enhanced resistance to
cracking. More details are given in Ref. [16].

3.3. Indentation curves

Two-layer Zr Si O coatings can be well characterized also by
the indentation curves of their individual layers, see Fig. 5. This
gure shows four combinations of the indentation curves of the
bottom brittle lm and the top elastic lm which prevent cracking
of the bottom brittle lm: (1) the lm 1 + the lm 4 (Fig. 5a), (2) the
lm 2 + the lm 4 (Fig. 5b), (3) the lm 1 + the lm 3 (Fig. 5c) and
(4) the lm 2 + the lm 3 (Fig. 5d). The properties of these lms are
given in Table 1. From Fig. 5 it is seen that
1. The areas between the loading and unloading curves of the brittle
bottom lms are greater than those of the elastic top lms; the
smaller area between curves means a higher elasticity of the lm.
2. In all coatings the top protective lm is elastic and harder than
the brittle bottom lm; the smaller maximum indentation depth
d means the higher hardness of the lm.
3. The top protective elastic lm can be as crystalline as X-ray
amorphous.
4. The bottom brittle lm can be also as crystalline as X-ray
amorphous.

Fig. 4. Surface morphology of two layer coating with brittle bottom layer and top elastic layer after bending of coated Mo strip around cylinder of radius r = 10 mm. (a)
the bottom layer is the lm No. 1 (amorphous), the top layer is the lm No. 4 (crystalline), (b) the bottom layer is the lm No. 2 (crystalline), the top layer is the lm No. 4
(crystalline), (c) the bottom layer is the lm No. 1 (amorphous), the top layer is the lm No. 3 (amorphous), and (d) the bottom layer is the lm No. 2 (crystalline), the top
layer is the lm No. 3 (amorphous). Physical and mechanical properties of the lms 1, 2, 3 and 4 are given in Table 1.

J. Musil et al. / Applied Surface Science 370 (2016) 306311

309

Fig. 5. Four combinations of the indentation curves of the bottom brittle lm and the top elastic lm which prevent cracking of the bottom brittle lm: (a) the lm 1 + the
lm 4, (b) the lm 2 + the lm 4, (c) the lm 1 + the lm 3 and (d) the lm 2 + the lm 3. Indentation curves were measured on the lms sputtered on Si (1 0 0) substrates.

5. The bottom brittle lm with the lower hardness than that of top
lm can be protected against cracking by the harder top lm. On
the other hand, the bottom brittle lm with the higher hardness
than that of top lm can be protected against cracking by the
softer top lm.
3.4. Optical transparency
Very interesting is the optical transparency of individual lms.
Therefore, the Zr Si O lms were also sputtered on glass substrates. The optical transparency was measured in a wide range of
wavelengths  from 250 to 800 nm. Results of these measurements
are given in Fig. 6. From this gure it is seen that while brittle lms
(the lm No. 1 and the lm No. 2) are opaque, the elastic lms are
well transparent. The opacity of the brittle lms is due to a large
amount of free Si and Zr atoms in the lm. The transparency of
the elastic lm with higher content of Si is practically the same as
that of the glass without lm and higher than that of the elastic
lm with the higher content of Zr. This difference is due to the fact
that the Zr Si O lm with higher Si content essentially represents
an SiO2 lm which almost completely eliminates reections at the
lm/glass substrate interface. This is a big advantage of the elastic
Zr Si O lm with high Si content. On the other hand, the disadvantage of this lm is its low hardness H 7 GPa. On the other hand, the
elastic Zr Si O lm with higher Zr content is the ZrO2 based lm
with lower optical transparency due to reections at the lm/glass
substrate interface but with a higher hardness H 17 GPa.
4. Low-temperature sputtering of exible nanocomposite
lms
At present, there is an urgent need to master the formation of crystalline or at least nanocrystalline exible lms on
heat sensitive substrates such as polymer foils, textiles, plastics,

Fig. 6. Transmittance of the brittle Zr Si O lms amorphous (lm 1) and crystalline (lm 2) and the elastic Zr Si O lms with enhanced resistance to cracking
amorphous (lm 3) and crystalline (lm 4) sputtered on glass substrate as a function
of wavelength of the electromagnetic wave.

polycarbonates, etc., without the substrate heating. It is a very

difcult and vitally important task because the formation of the
exible lms with enhanced resistance to cracking at low substrate
temperatures Ts 100 C is of a great potential for many advanced
applications, namely for the exible electronics, at panel displays,
micro-electromechanical (MEMS) systems, formation of the functional lms on polymer foils and fabrics, etc.
The formation of the exible lms on unheated substrates is
possible. It is based on the replacement of the equilibrium substrate
heating (Ts /Tm ) by the non-equilibrium atomic scale heating, i.e.
on the energy Ep delivered to the growing lm by condensing and

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J. Musil et al. / Applied Surface Science 370 (2016) 306311

Fig. 7. Schematic illustration of two dimensional (2D) Thorntons structural zone

model (SZM) extended into region of low-pressure sputtering. Adapted after Ref.
[22].

bombarding particles; here Tm is the melting temperature of the

material of the lm. The principle of formation of the exible lms
on unheated substrates is illustrated in Fig. 7. This gure represents
the two dimensional (2D) structural zone model (SZM) of sputtered
lms developed by Thornton [21] extended to low sputtering gas
pressures p 0.1 Pa [22]. The zone T of the SZM represents dense,
voids-free lms in compression ( < 0) with enhanced resistance to
cracking; here  is the macrostress in the lm.
From Fig. 7 it is clearly seen that just the zone T expands to low
values of the ratio Ts /Tm 0 with decreasing argon pressure pAr .
This means that the dense, voids-free lms with enhanced resistance to cracking in the zone T of the SZM can be formed without
the substrate heating by increasing of the energy Ep at low sputtering gas pressures p. The energy Ep can be delivered in the growing
lm either by the combined action of bombarding ions and fast neutrals (Ep = Ebi + Efn ) or by the fast neutrals only (Ep = Efn ). The energy
of bombarding ions Ebi is controlled by the substrate bias Us . On the
contrary, the energy of condensing fast neutrals Efn is controlled by
the sputtering gas pressure pAr and is increased by decreasing of
the sputtering gas pressure pAr . The whole kinetic energy of these
particles is transferred to the growing lm and stimulates its densication and nano-crystallization. This means that the formation of
the exible, dense, voids-free sputtered lms with enhanced resistance to cracking on unheated substrates based on the replacement
of the conventional heating (Ts ) with the atomic scale heating (Ep )
is possible [22]. There are two key parameters which decide on
the formation of such lms: (1) the energy Ep and (2) the melting
temperature Tm of created lms. More details can be found in Refs.
[13,14,2326].
In summary, it can be concluded that the lms with dense, voidsfree microstructure, compressive macrostress ( < 0) and enhanced
resistance to cracking can be formed in the zone T of the Thorntons SZM also at low substrate temperatures Ts 100 C, i.e. at low
values of Ts /Tm ratio, when sufcient energy Ep is delivered to the
growing lm by bombarding ions and/or when a low sputtering
gas pressure p is used. Very important role in the low-temperature
sputtering of the exible lms plays also the melting temperature
Tm of the lm material which (i) decides on the value of Ts /Tm
ratio and (ii) can be controlled by the addition of selected elements
in the lm.
5. Conclusions
The investigation reported in this article shows that the brittle
lm can be protected against cracking when it is over-coated with
the elastic top lm. It was found that (i) the brittle lms exhibit low

elastic recovery We < 60% and low ratio H/E* 0.1 and can be either
X-ray amorphous or crystalline, (ii) the elastic top lms exhibit high
elastic recovery We 60% and high ratio H/E* 0.1 and also can be
either X-ray amorphous or crystalline, and (iii) the cracking of the
brittle lm can be prevented when it is over-coated with the elastic
top lm. The last nding is of key importance not only for the deepening of the present knowledge in the eld of two-layer coatings
but also for many applications. Many functional coatings are brittle
and easily crack when they are (i) deposited on the exible substrates or (ii) bended and thus their function can be interrupted.
Therefore, the overlapping of the brittle lm by the elastic top lm
(over-layer) is a very efcient tool which ensures the reliable function of the brittle lm even in the case when it is deposited on
the exible substrate. These conclusions are applicable also to the
lms on plastic substrates and the thick multilayer coatings with
alternating brittle/elastic bi-layers.

Acknowledgement
This work was supported by the project LO1506 of the Czech
Ministry of Education, Youth and Sports.

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