Professional Documents
Culture Documents
Applied Surface Science: J. Musil, J. Sklenka, R. Cerstv y
Applied Surface Science: J. Musil, J. Sklenka, R. Cerstv y
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
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.
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
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).
308
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].
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.
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.
310
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.
References
[1] J.S. Koehler, Attempt to design a strong solid, Phys. Rev. B: Condens. Matter 2
(1970) 547.
[2] B.-S. Yau, J.-L. Huang, H.-H. Lu, P. Sajgalik, Investigation of
nanocrystal-(Ti1x Alx )Ny /amorphous-Si3 N4 nanolaminate lms, Surf. Coat.
Technol. 194 (2005) 119127;
Y. Dong, W. Zhao, J. Yue, G. Li, Crystallization of Si3 N4 layers and its inuence
on the microstructure and mechanical properties of Zr/Si3 N4
nanomultilayers, Appl. Phys. Lett. 89 (2006) 121916.
[3] S.H. Tsai, J.G. Duh, Microstructure and mechanical properties of CrAlN/SiNx
nanostructured multilayered coatings, Thin Solid Films 518 (2009)
14801483.
[4] F. Li, S. Zhang, J. Kong, Y. Zhang, W. Zhang, Multilayer DLC coatings via
alternating bias during magnetron sputtering, Thin Solid Films 519 (2011)
49104916.
[5] J. Zhang, B. Zhang, Q. Xue, Z. Wang, Ultra-elastic recovery and low friction of
amorphous carbon lms produced by a dispersion of multilayer graphene,
Diamond Relat. Mater. 23 (2012) 59.
[6] Y.X. Wang, S. Zhang, J.-W. Lee, W.S. Lew, D. Sun, B. Li, Hard yet tough ceramic
coating: not a dream any more via nanostructured multilayering, Nanosci.
Nanotechnol. Lett. 4 (2012) 378383.
[7] J. Zheng, J. Hao, X. Liu, Q. Gong, W. Liu, A thick TiN/TiCN multilayer lm by DC
magnetron sputtering, Surf. Coat. Technol. 237 (2013) 110116.
[8] T.P. Soares, C. Aguzzoli, G.V. Soares, C.A. Figueroa, I.J.R. Baumvol,
Physicochemical and mechanical properties of crystalline/amorphous
CrN/Si3 N4 multilayers, Surf. Coat. Technol. 237 (2013) 170175.
[9] Y. Zhang, Y. Zhai, F. Li, S. Zhang, P. Zhang, S. Zhang, Effect of microstructure
and mechanical properties diference between sub-layer on performance of
alternate hard and soft diamond-like carbon multilayer lms, Surf. Coat.
Technol. 232 (2013) 575581.
[10] Y.C. Chan, H.W. Chen, J.G. Duh, J.W. Lee, Texture, microstructure and
tribological behavior in TiAlN/SiNx multilayers, Int. J. Appl. Ceram. Technol. 11
(2014) 611617.
[11] M. Nakatani, J. Nishimura, S. Hanaki, H. Uchida, Crack-healing behavior
induced by oxidation in SiN/SiC nanolaminated lms, Thin Solid Films 556
(2014) 6873.
[12] J.J. Roa, E.J. Pique, R. Martinez, G. Ramirez, J.M. Tarrago, R. Rodriguez, L. Llanes,
Contact damage and fracture micromechanims of multilayered TiN/CrN
coatings at micro- and nano-length scales, Thin Solid Films 571 (2014)
308315 (Part 2).
[13] J. Musil, Hard nanocomposite coatings: thermal stability, oxidation resistance
and toughness, Surf. Coat. Technol. 207 (2012) 5065.
[14] J. Musil, Flexible hard nanocomposite coatings, RSC Adv. 5 (2015)
6048260495.
[15] J. Musil, Advanced hard nanocomposite coatings with enhanced toughness
and resistance to cracking, in: S. Zhang (Ed.), Chapter 7 in Thin Films and
Coatings: Toughening and Toughness Characterization, CRC Press, USA, 2015,
pp. 375463.
[16] J. Musil, J. Sklenka, J. Prochzka, Protective over-layer coating preventing
cracking of thin lms deposited on exible substrates, Surf. Coat. Technol. 240
(2013) 275280.
311