http://www.paper.edu.

cn

Amorphous film of high entropy alloy deposited by direct

current magnetron sputtering#
LI Jianchen, ZHU Jianbo*

(Department of Materials Science and Engineering, Jilin University, Changchun 130021)

10

15

Abstract: In this paper, The amorphous films of AlFeCoNiCuZrV multicomponent high-entropy alloy
were deposited by direct current magnetron sputtering in the mixture atmosphere of Ar and O 2. The
results demonstrate that the chemical composition, microstructure, and mechanical properties of the
amorphous films intimately rely on the concentration of O 2 in the atmosphere mixture. When O2 flow
ratio increases from 0 to 50%, the thickness of the films decreases, whereas the roughness firstly
decreases and then increases. At the O2 flow ratio of 30%, a perfect dense and smooth amorphous
nitride film could be achieved. While the hardness and Youngs modulus of the film reach the
maximum values of 12 and 166 GPa, respectively.
Key words: High entropy alloy; amorphous film; properties; magnetron sputtering

0 Introduction

20

25

30

35

40

The conventional alloys generally consist of one principal element associated with a
substantial amount of other elements to enhance the properties and processing [1], which differ
from the high-entropy alloy (HEA) recently proposed by Yeh et al. [2, 3]. HEA is a novel concept
for the alloy system that has multiple principal elements with equimolar or near-equimolar ratios
in the rang of 5-35 at.%. In recent years, HEA films have been widely studied, such as TiVCrZrHf
film [4], AlCrMoTaTiZr film [5, 6], etc. Moreover, HEA films have been proposed for the
potential applications as protective films [7-9], wear-resistant materials [10], corrosion-resistant
materials [11], and coatings in communication devices [12]. That is due to their interesting
properties, such as high hardness [13], strength [14, 15], wear resistance [16, 17], and
microstructure stability against heat treatment [18-20].
It is known that the transition metal nitride and oxide coatings are usually much harder, more
chemically inert, but brittler than the original metals or alloys. This has stimulated recent
explorations for improving the mechanical properties of alloys. In previous work [21, 22], we have
developed the novel HEA alloys (i.e. FeCoNiCu system) with a single FCC crystalline structure,
which exhibits good plastic properties with the tensile strain up to 18%. Musil et al. reported the
hard and super-hard Zr-Ni-N nanocomposite films with the hardness of 40 GPa [23]. The similar
strengthening effect was also revealed in VN [24]. Moreover, the addition of other element, such
as Al, was found to further improve the thermal stability of the film [25, 26]. Based on the above
observations, the multicomponent FeCoNiCuVZrAl film is expected to possess excellent
mechanical properties.
In this contribution, the amorphous films of AlFeCoNiCuZrV HEA are prepared by using
direct current magnetron sputtering system at a low depositing temperature. The amorphization
occurs probably due to the enhanced glass-forming ability for the alloys containing more than
three elements [27], as well as the limited diffusion of the elements at the low depositing
temperature [28]. In addition, the composition, microstructure, hardness and Young modulus of
the amorphous film were systematically investigated and discussed.

Foundations: NNSFC (Grant No. 50571040); National Foundation of Doctoral Station (Grant No.
20100061110019)
Brief author introduction:Li Jianchen(1957-), Male, Professor,Main research: Metal materials. E-mail:
ljc@jlu.edu.cn

-1-

http://www.paper.edu.cn

1 Experimental methods
45

50

55

60

The AlFeCoNiCuZrV HEA was melted for at least 5 times by the arc melting-method under a
purified argon gas atmosphere. Then, it was shaped into a disc of 60 mm in diameter and 5 mm in
thickness as a target. Table 1 lists the composition of the target and the atomic ratios of each
element measured by energy dispersive spectrometry (EDS). Quartz glass wafers were cleaned
sequentially in de-ionized (DI) water, acetone and DI water, for the following deposition of the
nitride films of AlFeCoNiCuZrV by DC magnetron sputtering. In a mixture atmosphere of Ar and
N2, the nitride films with the thickness of about 12 m were deposited under a plasma power of
30 W, a constant working pressure of 0.9 Pa, a substrate bias of 98 V, a deposited time of 2 hours
at room temperature. The distance between the substrate and the target was set as 75 mm. The
nitrogen flow ratio RN = O2/(Ar+O2) was precisely adjusted by varying the O2 flow rate from 0 to
30 sccm with a constant Ar flow rate of 30 sccm. The phase structure analysis of the target and
nitride films was performed on Rigaku D/max 2500 X-ray diffractometer at 50 KV and 250 mA
(XRD, D/Max 2500pc) with the scanning angles ranging from 20 to 90 degree at a scanning rate
of 2 degree/min. Both the surface morphology and thickness of the deposited films were observed
by field-emission scanning electron microscopy (FESEM, JEOL JSM 6700F). The chemical
compositions of the films were analyzed by EDS. The hardness and Youngs modulus of the films
were measured by a nanoindenter (XP nanomechanical testing system, MTS Corporation), during
which the penetration depth of the indenter was controlled at about 1/10 of the film thickness to
avoid substrate effect.
Table 1 Composition of the AlFeCoNiCuZrV high-entropy alloy target (at.%)

65

70

75

80

85

Element

Fe

Co

Ni

Cu

Zr

Al

Nominal composition

14.28

14.28

14.28

14.28

14.28

14.28

14.28

Composition By EDS

13.96

13.95

13.20

13.83

14.57

15.19

15.31

2 Results and discussion

Fig. 1 shows the XRD pattern of the target of AlFeCoNiCuZrV HEA. As indicated, the
crystalline structures are composed of (cubic), (cubic) and (monoclinic) phases with the
space group of Fm3m (225), Im3m (229) and C2/m(12), respectively. Fig. 2 illustrates the XRD
patterns of the films of AlFeCoNiCuZrV alloy deposited under different O2 flow ratios (RN). It can
be clearly seen that all the films exhibit amorphous structure, dramatically different from that of
the as-melted HEA target shown in Fig. 1. This phenomenon was also observed in the preparation
of the nitride films of the AlCrSiTiV [29], AlCrMoSiTi [30], and AlMoNbSiTaTiVZr [31], the
oxide films of AlCoCrCu0.5NiFe [32] and AlCrTaTiZr HEA [33].
The formation of the amorphous films during the fabrication is reasonable according to the
rules proposed by Inoue [27] that the glass-forming ability can be strengthened for
multicomponent systems. From a thermodynamical point of view, the large glass-forming ability
is obtained under the condition of low Gibbs free energy G (T) for the transformation from liquid
to crystalline phase, where G = Hf - TSf with Hf and Sf being the enthalpy and entropy of
fusion, respectively. According to the above equation, the low G value is obtained in the case of
low Hf and large Sf. The large Sf is expected to be obtained in multicomponent alloy systems,
because Sf is proportional to the number of microscopic states. The G at a constant temperature
also decreases in the cases of low chemical potential caused by the low enthalpy, high reduced
glass transition temperature, and large solid/liquid interface energy. Based on these
thermodynamical considerations, it can be concluded that the multicomponent increases the dense
random packing, which is favor of the decrease of Hf and the increase of solid/liquid interface
-2-

90

http://www.paper.edu.cn

energy. This is consistent with the result that a larger glass-forming ability has been obtained for
the above multicomponent systems. In conclusion, the low enthalpy, the great difference between
the depositing temperature of films and the glass transition temperature, and the large solid/liquid
interface energy benefit the formation of the amorphous films. From Fig. 2, we can find that the
film without oxygen is also amorphous. Thus, the RN has almost no effect on the amorphous
formation. However, the RN has great effects on the chemical compositions, thickness,
morphology, hardness and Young's Modulus of the films, which will be discussed later.

Fig. 1 X-Ray diffraction curve of the AlFeCoNiCuZrV target.

1000
900

50%

800
Intensity(CPS)

700
30%

600
500
400

10%

300
200
0%

100
0
20

95

40

60

80

100

Fig. 2 X-Ray diffraction curves of the AlFeCoNiCuZrV films deposited under different O2 flow ratios (RN).

100

105

Fig. 3 shows the chemical compositions of the multicomponent AlFeCoNiCuZrV films

deposited under different RN. When RN = 0, the concentration (atomic ratio) of each metallic
element in the film is rather close to that in the AlFeCoNiCuZrV target, whose composition is
listed in Table 1. Oxygen concentration in the film rises sharply to 55 at.% when the oxygen flow
ratio (R0) is set to 2.5%. Compared with nitride films prepared based on the same alloy, where the
concentration of nitrogen was only 39 at.% at a much higher flow ratio of 9%, it is seen that
oxygen has a much stronger tendency to react with the individual metal atoms than nitrogen does.
This is supported by the significantly larger heat of formation of the metal oxides relative to
corresponding metal nitrides. For example, the heat of formation of TiN is only 338 kJ/mol [34],
while that of TiO2 is 944 kJ/mol [35]. When R0 is further increased, concentration of oxygen
also increases and then saturates near 67 at.%.

-3-

http://www.paper.edu.cn

80
Al
V
Fe
Co
Ni
Cu
Zr
O

70
Concentration (at%)

60
50
40
30
20
10
0

10

20

30

40

50

O2/(O2/Ar)ratio(%)

Fig. 3 Chemical compositions of the AlFeCoNiCuZrV films deposited under different O2 flow ratios (RN).

110

115

120

Table 2 gives the thickness of the AlFeCoNiCuZrV films deposited under different RN. The
largest and smallest thicknesses are 2.100 m (RN = 0) and 0.875 m (RN = 50%), respectively. It
is also found that the thicknesses of the films decrease with the increasing RN. This originates from
the formation of the oxide film at the target surface due to the good affinity of all the target
elements with oxygen, which hinders the atoms from sputtering. It is a typical result of target
poisoning [36]. Additionally, oxygen ions are known as less effective as argon ions for sputtering
[36]. Therefore, as the two gas species have comparable collision cross-sections for ionization [37],
a greater proportion of the target current will be carried by oxygen ions at higher oxygen partial
pressures, inducing the decrease in the sputtering rate. Moreover, when more O2 are added, more
metallic oxide are formed on the substrate, which enhances the internal stress of the film and
inhibits the growth. Another aspect is probably due to the fact that more metallic oxide is pumped
out of deposition chamber along with exhaust gas [32].
Table 2 Thickness of the AlFeCoNiCuZrV films deposited under different O2 flow ratios (RN).

125

130

135

RN

10%

30%

50%

Thickness (m)

6.450

3.545

2.432

1.725

Fig. 4 shows the top-view FESEM images of the AlFeCoNiCuZrV films deposited under
different RN, illustrating the evolution of morphology. It can be see that the films are composed of
nanoparticles with different geometric morphology as RN changes. When RN = 0, an amount of
nanoparticles with the size of about 10 to 25 nm gather together, as shown in Fig. 4(a). With
increasing RN, the surface of the film becomes smoother and forms a smooth coating [see Fig.
4(b)]. Fig. 4(c) shows a morphology for a perfect dense amorphous AlFeCoNiCuZrV film
obtained at RN = 30%, where the surface is much smoother and cleaner than other films. This
decrease in the roughness at the higher nitrogen flow rate could be attributed to the reduction in
the arrival rate of the sputtered species, which can be reflected by the decrease of the film
thickness and corresponds to the structure zone models [38, 39]. There is more energy of per
depositing atom that leads to the formation of denser coatings with reduced surface roughness.
However, when the RN is increased to 50%, the surface become rougher [Fig. 4(d)], and the dense
amorphous coating seems to be destructed. That is because with further increasing RN, the target
poisoning is enhanced and the arrival rate of the sputtered species becomes so low that there are
not enough sputtered species arriving at the substrate. Therefore, the film surfaces become looser
and have more micro-holes. Therefore, RN of 30% is the just right ratio to form the smooth and
dense amorphous AlFeCoNiCuZrV film.
-4-

140

145

150

http://www.paper.edu.cn

(a)

(b)

(c)
(d)
Fig. 4 FESEM morphology of the AlFeCoNiCuZrV films deposited under different O2 flow ratios (RN): (a) RN = 0;
(b) RN = 10%; (c) RN = 30%; (d) RN = 50%.

Fig. 5 plots the hardness and Youngs modulus of the AlFeCoNiCuZrV films as a function of
RN. For the AlFeCoNiCuZrV film without the addition of O2, the hardness and Youngs modulus
are 8.6 and 153 GPa, respectively. They are relatively superior to typical films of pure metals and
alloys, which is mainly caused by the great solid-solution strengthening effect from the addition of
a large amount of different-size atoms. With addition of O2, the hardness and modulus increase
and reach maximum values of 12 and 166 GPa for the film deposited at RN = 30%. That might be
due to the perfect dense and smooth amorphous structure. With further increasing RN, the surface
becomes rougher and looser, as shown in Fig. 4(d). Meanwhile the micro-holes among particles
increase in size. Therefore, the hardness and modules decrease.
20

185
Hardness
Young's Modulus

180
175

16

170
165

14

160

12

155
150

10
8

155

Young's Modulus

Hardness (Gpa)

18

145
0

10

20

30

40

50

140

O2/(O2+Ar)ratio (%)

Fig. 5 Hardness and Young's Modulus of the AlFeCoNiCuZrV films deposited under different O2 flow ratios (RN).
-5-

http://www.paper.edu.cn

3 Conclusion

160

165

170

175

180

185

190

195

200

205

210

215

The films of AlFeCoNiCuZrV high-entropy alloy have been deposited successfully using
direct current magnetron sputtering. All the films exhibit amorphous structure, dramatically
different from the as-melted HEA target. The morphology and mechanical properties of these
amorphous films depend on the oxygen flow ratio. The thickness of films decreases with the
increasing O2 flow ratio. The biggest and smallest thicknesses are 2.100 m (RN = 0) and 0.875
m (RN = 50%), respectively. a perfect dense and smooth amorphous film is obtained with the
hardness and Youngs modulus up to the maximum values of 12 and 166 GPa, respectively.
References
[1] Handbook Committee. Metals nadbook[Z]. Metals Park, OH: ASM International, 1990.
[2] YEH J W,CHEN S K, LIN S J, GAN J Y, CHIN T S, SHUN T T,TSAU C H, CHANG S Y. Nanosctructured
high entropy alloys with multiple principal elements: novel alloy design concepte and outcomes [J]. 2004, 6:
299-303
[3] HUANG P K, YEH J W, CHEN T T, CHEN S K.Multi-principal-element alooys with improved oxidation and
wear resistance for thermal spray coating[J]. Adv. Eng, Mater., 2004, 6: 74-78.
[4] LIANG S C, TSAI D C, CHANG Z C, SUANG H S, LIN Y C, YEH J W, DENG M J, SHIEU F S. Structural
and mechanical properties of multi-element (TiVCrZrHf) coating by reactive magnetron sputtering [J]. Appl, Surf.
Sci., 2011, 258: 399-403.
[5] CHENG K H, LAI C H, LIN S J, YEH J W. Structureal and mechanical properties of multi-element
(AlCrMoTaTiZr)Nx coating by reactive magnetron sputtering [J]. Thin Sold Films, 2011, 519: 3185-3190.
[6] LIANG S C, CHANG Z C, TSAI D C, LIN Y C, SUNG H S, DENG M J, SHIEU F S. Effect of substrate
temperature on the structure and mechanical properties of (TiVCrZrHf)N coatings [J]. Appl. Surf. Sci., 2011, 257:
7709-7713.
[7] TSAI M H, YEH J W, GAN J Y.Diddusion barrier properties of AlMoNbSiTaTiVZr high entropy alloy layer
between copper and silicon [J]. Thin Solid Films, 516: 5527-5530.
[8] CHEN T K, SHUN T T, YEH J W, WONG M S. Nanosreuctured nitrid films of multi-element high entropy
alloys by reactive DC sputtering [j]. Suf. Coat. Technol., 2004, 188-189: 193-200.
[9] CHANG S Y, CHEN D S. (AlCrTaTiZr)N/(AlCrTaTiZr)N-0.7 bilayer structure of high resistance to the
interdiffusion of Cu and Si at 900 degrees C [J]. Mater. Chem. Phys., 2011, 125: 5-8.
[10] REN B, LIU Z X, SHI L, CAI B, WANG M X. Structure and properties of (AlCrMnMoNiZrB0.1)Nx coating
prepared by reactive DC sputtering [J]. Appl. Surf. Sci., 2011, 257: 7172-7178.
[11] CHEN Y Y, DUVAL T, HUNG U D, YEH J W, SHIH H C. Structure and electrochenical properties of high
entropy alloys - a comparison with type-304 stainless steel [J]. Corros. Sci., 2005, 47: 2257-2279.
[12] CHEN H K, LI S H, DUH J G. Structure and soft magnetic properties of Fe-Co-Ni-based multicomponent
thin films [J]. J Electron. Mater., 2005, 34: 1480-1483.
[13] ZHOU Y J, ZHANG Y, WANG Y L, CHEN G L. Microstructure and compressive properties of
multicomponent Alx(TiVCrMnFeCoNiCu)100-x high entropy alloys [J]. Mater. Sci. Eng. A, 2007, 454-455:
260-265.
[14] ZHOU Y J, ZHANG Y, WANG Y L, CHEN G L. Solid solution alloys of AlCoCrFeNiTix with excellent
room temperature mechanical properties [J]. Appl. Phys. Lett., 2007, 90: 181904
[15] HU Z H, ZHAN Y Z, ZHANG G H, SHE J, LI C H. Effect of rare earth Y addition on the microstructure and
mechanical properties of high entropy AlCoCrNiTi alloys [J]. Mater. Des., 2010, 31: 1599-1602.
[16] HSU C Y, SHEN T S, YEH J W. Effect of iron content on wear behavior of AlCoCrFexMo0.5Ni high
entropy alloys [J]. Wear, 2010, 268: 653-659.
[17] HUANG C, ZHANG Y Z, VILAR R, SHEN J Y. Dry sliding wear behavior of laser clad TiVCrAlSi high
entropy alloy coating on Ti-6Al-4V substrate [J]. mATER. dES., 2012, 41: 338-343.
[18] REN B, LIU Z X, CAI B, WANG M X. Aging behavior of CuCr2Fe2NiMn high entropy alloy [J]. Mater.Des.,
2012, 33: 121-216.
[19] TSAI C W, CHEN Y L, TSAI M H, YEH J W, SHUN T T, CHEN S K. Deformation and annealing behavior
of high entropy alloy Al0.5CoCrFeNi [J]. J Alloy Compd., 2009, 486: 427-435.
[20] SENKOV N, WILKS G B, MIRACLE D B, CHUANG C P, LIAW P K. Refractory high entropy alloys [J].
Intermetallics, 2010, 18: 1758-1765.
[21] LIU L, ZHU J B, ZHANG C, LI J C, JIANG Q. Microstructure and properties of FeCoCuNiSnx high entropy
allos [J]. Mater. Sci. Eng. A, 2012, 548: 64-68.
[22] LIU L, ZHU J B, ZHNAG C, LI J C, JIANG Q. Microstructure and tensile properties of FeMnNiCuCoSnx
high entropy alloys [J]. Mater. Des., 2013, 44: 223-227.
[23] MUSIL J, KARVANKOVA P, KASL J. Ward and superhard Zr-Ni-N nanocomposite films [J]. Surf. Coat.
Technol., 2001, 139: 101-109.
[24] UCHIDA M, NIHIRA N, MITSUO A, TOYODA K. Friction and wear properties of CrAlN and CrVN films
deposited by cathodic arc ion plating method [J]. Surf. Coat. Technol., 2004, 177-178: 627-630.
-6-

220

225

230

235

240

245

http://www.paper.edu.cn

[25] KIM C W, KIM K H. Anti-oxidation properties of TiAlN film prepared by plasma-assisted chemical vapor
deposition and roles of Al [J]. Thin Solid Films, 1997, 307: 113-119.
[26] LAI C H, LIN S J, YEH J W, CHANG S Y. Prepationg and characterization of AlCrTaTiZr multi-element
nitride coatings [J]. Surf. Coat. Technol., 2006, 201: 3275-3280.
[27] INOUE A. High strength bulk amorphous alloys with low cooling rates [J]. Mater. Trans. JIM, 1995, 36:
866-875.
[28] GUO S, LIU C T. Phase stability in high entropy allys: Formation of solid-solution phase or amorphous phase
[J]. Prog. Nat. Sci., 2011, 21: 433-446.
[29] TSAI C W, LAI S W, CHENG K H, TSAI M H, DAVISON A, TSAU C H, YEH J W. Strong amorphization
of high entropy AlBCrSiTi nitride film [J]. Thin Solia Films, 2012, 520: 2613-2618.
[30] LIU L, ZHU J B, LI J C, JIANG Q. Dense and smooth amorphous films of multicomponent FeCoNiCuVZrAl
high entropy alloy deposited by direct current magnetron sputtering [J]. Mater. Des., 2013, 46: 675-679.
[31] CHANG H W, HUANG P K, DAVISON A, YEH J W, TSAU C H, YANG C . Nitride films deposited from
an eqimolar Al-Cr-Mo-Si-Ti alloy target by reactive direct current magnetron sputtering [J]. Thin Solid Films,
2008, 516: 6402-6408.
[32] HUANG Y S, CHEN L, LUI H W, CAI M H, YEH J W. Microstructure, hardness, resistivity and thermal
stability of sputtered oxide films of AlCoCrCu0.5NiFe high entropy alloy [J]. Mater. Sci. Eng. A, 2007, 457:
77-83.
[33] LIN M I, TSAI M H, SHEN W J, YEH J W. Evolution of structure and properties of multi-component
(AlCrTaTiZr)O-x films [J]. Thin Solid Films, 2010, 518: 2732-2737.
[34] PIERSON H O. Handbook of refractory carbides and nitrides[Z]. New Jersey: Noyes Publications, 1996.
[35] DEAN J A. Lange's handbook of chenistry [Z]. New York: Mcgraw Hill, 1999.
[36] MASON R M, PICHILING M. Sputtering in a glow discharge ion source-pressure dependence: theory and
experiment [J]. J Phys. D, 1994, 27: 2363-2371.
[37] CHAPMAN B N. Glow discharge processes [Z]. New York: John Wiley & Sons, 1980.
[38] THORNTON J A. The microstructure of sputter-deposited coatings [J]. J Vac. Sci. Technol. A, 1986, 4:
3059-3066.
[39] MESSIER R, VENUGOPAL V C, SUNAL P D. Origin and evolution of aculptured thin films [J]. J Vac. Sci.
Technol. A, 2000, 18: 1538-1545.

250

255

130021
Ar O2 AlFeCoNiCuZrV
0-50%
O2 30%
12GPa 166 GPa

TG113

-7-