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Materials Science and Engineering A 457 (2007) 7783

Microstructure, hardness, resistivity and thermal stability of sputtered


oxide films of AlCoCrCu0.5NiFe high-entropy alloy
Yuan-Sheng Huang a, , Ling Chen b , Hong-Wei Lui c , Ming-Hong Cai d , Jien-Wei Yeh d
a

Department of Materials Technology, Jiangmen Polytechnic, Jiangmen 529000, Guangdong, PR China


College of Mechanical Engineering, South China University of Technology, Guangzhou 510640, PR China
c College of Mechanical Engineering, Guangxi University, Nanning 530004, PR China
d Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 300, Taiwan, ROC
b

Received 14 September 2006; received in revised form 30 November 2006; accepted 1 December 2006

Abstract
The sputtered oxide films of AlCoCrCu0.5 NiFe high-entropy alloy were deposited on the silicon wafer using radio frequency sputter system,
and subsequently were annealed at 500, 700 or 900 C. Surprisingly, the sputtered films are of simple structure. With no oxygen addition to the
working gas, the AlCoCrCu0.5 NiFe high-entropy alloy film is amorphous. When the oxygen content in the working gas is between 10 and 50%, the
sputtered oxide films are HCP with lattice constants of a = 0.3583 nm and c = 0.4950 nm. Before annealing, both the resistivity and thickness of the
oxide film decrease with increasing oxygen content and the hardness value reaches maximum at 30% O2 . No new phases in the oxide films form
during annealing, indicating the oxide films are very stable at high temperature. However, the crystal grains tend to grow up and the micro-hole
size among grains increases with the annealing temperature. The resistivity of the oxide film steps up with annealing temperature, whereas the
hardness value decreases. The oxide-film thickness changes very little during annealing.
2006 Elsevier B.V. All rights reserved.
Keywords: High-entropy alloy; Oxide film; Microstructure; Resistivity; Hardness

1. Introduction
In the past the practical alloy systems were based mainly
on one principal element as the matrix even though a
substantial amount of other elements was incorporated for
property/processing enhancement [1,2]. Metallurgists confined
themselves to systems where the number of alloying elements
was limited in any one phase. This was partly because as alloys
are made with an increasing number of component metals, many
intermetallic compounds and complex microstructures form and
the database necessary in terms of phase diagram information
increases sharply [3,4]. However, this impasse has been broken with three startling discoveries of recent vintage. Metals are
mixed in a multi-metallic cocktail to make bulk metallic glasses
[5,6], multi-functional, superelastic and superplastic alloys [7]
and nano-structured high-entropy alloys [3]. In 2003, Saito et
al. [7] announced the discovery of a multi-functional alloy with
compositions such as Ti23Nb0.7Ta2Zr1.2O alloy.

Corresponding author. Tel.: +86 750 3021406; fax: +86 750 3501211.
E-mail address: nightofgz@163.com (Y.-S. Huang).

0921-5093/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2006.12.001

High-entropy alloys were developed in recent years by Yeh


et al. [3,8]. Nano-structured high-entropy alloys with multiple
principal elements are of equimolar or near-equimolar ratios
and concentrations between 35 and 5 at.%. High-entropy alloys
might possess simple crystal structures, ease of nanoprecipitation, and promising properties in high hardness and superior
resistance to temper softening, wear, oxidation and corrosion [920]. Following Boltsmanns hypothesis the relationship
between the entropy and system complexity, the change in configurational entropy during the formation of a solid solution from
three elements with an equimolar ratio is already larger than
the entropy changes for fusion of most metals. Consequently,
alloys containing a higher number of principal elements will
more easily yield the formation of random solid solutions during solidification, rather than intermetallic compounds or other
complicated phases [1012]. Mackay [21] had reported that the
number of intermetallics as a function of components increases
at first but drops off after four components. Solid solutions
with multi-principal elements will tend to be more stable at elevated temperatures because of their large mixing entropies [20].
AlCoCrCu0.5 Ni, Alx CoCrCuFeNi, AlCoCrCuFeMoNiTiVZr,

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Y.-S. Huang et al. / Materials Science and Engineering A 457 (2007) 7783

Fig. 1. XRD patterns of: (a) target, (b) AlCoCrCu0.5 FeNi alloy film, (c) oxide
film deposited at CO2 = 10%, (d) oxide film at CO2 = 30%, and (e) oxide film
at CO2 = 50%.

AlCoCrFeMo0.5 NiSiTi and AlCrFeMo0.5 NiSiTi high-entropy


alloys are examples exhibiting a quite simple as-cast microstructure and promising properties [10,1316]. Among the previous
alloys investigated, the AlCoCrCu0.5 NiFe alloy is of BCC
structure. Most present and former oxide-film systems were
synthesized with targets that are based mainly on one principal matrix element. In this paper, oxide film was deposited
with the AlCoCrCu0.5 FeNi high-entropy alloy target using radio
frequency sputter system, and its structure and some properties were measured. Surprisingly, the sputtered oxide films of
AlCoCrCu0.5 FeNi high-entropy alloy are of simple structure and
have rather fine properties and a good thermal stability.
2. Experimental details
The AlCoCrCu0.5 FeNi high-entropy alloy was prepared by
the arc melting and casting method, and then was made into
target. Refer to [9] for further details of this preparation method.
The sputtered oxide films of AlCoCrCu0.5 FeNi high-entropy
alloy were deposited on Si (1 0 0) single crystal wafers and glass
(microscopic slides) using radio frequency sputter system. The
silicon wafers and glass were cleaned with water and acetone

Fig. 2. XRD patterns of the oxide film deposited at CO2 = 10%: (a) before
annealing, (b) annealed at 500 C, (c) annealed at 700 C, and (d) annealed at
900 C.

Fig. 3. XRD patterns of the oxide film deposited at CO2 = 30%: (a) before
annealing, (b) annealed at 500 C, (c) annealed at 700 C, (d) annealed at 900 C.

Fig. 4. XRD patterns of the oxide film deposited at CO2 = 50%: (a) before
annealing, (b) annealed at 500 C, (c) annealed at 700 C, (d) annealed at 900 C.

prior to deposition. The power on the AlCoCrCu0.5 FeNi target


was 150 W. The depositions were performed at a total pressure
of 103 Torr in a mixed Ar and O2 atmosphere. The ratio
between the oxygen partial pressure and the total working
gas pressure (CO2 = pO2 /(pO2 + pAr )) was varied from 0 to
50% in order to obtain different oxygen concentrations in the
films. The substrate temperature was kept constant at 573 K.
Anneal was carried out on a vacuum furnace. Both the surface

Fig. 5. TEM morphology and EDP of the typical oxide film deposited at CO2 =
30%.

Y.-S. Huang et al. / Materials Science and Engineering A 457 (2007) 7783

morphology and film thickness of the sputtered films were


observed with scanning electron microscope (SEM, JEOL
JSM-5410). The chemical compositions were analyzed by SEM
energy dispersive spectrometry (EDS). An X-ray diffractometer
(XRD, Rigaku ME510-FM2, Tokyo, Japan) was used for the
identification of structure, with the 2 scan ranging from 20 to
90 at a rate of 0.5 min1 . The radiation was from a 30 kV,
20 mA copper target. The resistivity of the oxide films was
measured using four-point probe (Keithley Model 236). The
film hardness was analyzed using micro/nanoindention tester
(CSM, Swiss) and represented with Vickers hardness value.
Thin-foil specimens were prepared by mechanical thinning
followed by ion milling at room temperature, and subsequently
were observed under a transmission electron microscope (TEM,
JEOL JEM-100CXII, Tokyo, Japan).
3. Results and discussion
3.1. XRD and TEM analysis
Fig. 1 shows the XRD patterns of the sputtered alloy film or
oxide films of AlCoCrCu0.5 NiFe high-entropy alloy. The XRD
pattern of AlCoCrCu0.5 FeNi alloy target is also provided in

79

Fig. 1. It is clear that the target is of BCC structure. When no


oxygen is added to the working gas, the AlCoCrCu0.5 FeNi alloy
film is amorphous. When the oxygen content in the working gas
is between CO2 = 10 and 50%, the sputtered oxide film is HCP.
The lattice constants of the HCP phase are a = 0.3583 nm and
c = 0.4950 nm. When the oxygen content increases from CO2 =
30 to 50%, XRD peaks become lower and broader, indicating
grains tend to have a smaller size (about 8.12 nm determined by
Scherrer expressions).
The sputtered oxide films of AlCoCrCu0.5 NiFe high-entropy
alloy were annealed at different temperature, and subsequently
were analyzed by XRD. The XRD results are shown in
Figs. 24. It is seen that after annealing, the oxide films are of
HCP structure. No obvious phase transformation in the oxide
films occurs during annealing. It is obvious that the oxide film
has a good thermal stability. This is similar to high-entropy
alloys, that is, following Boltsmanns hypothesis the relationship between the entropy and system complexity, the change
in configurational entropy during the formation of a solid
solution from three elements with an equimolar ratio is already
larger than the entropy changes for fusion of most metals.
Consequently, alloys containing a higher number of principal
elements will more easily yield the formation of random solid

Fig. 6. SEM morphology of the oxide film deposited at CO2 = 10%: (a) before annealing, (b) annealed at 500 C, (c) annealed at 700 C, (d) annealed at 900 C.

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Y.-S. Huang et al. / Materials Science and Engineering A 457 (2007) 7783

solutions during solidification, rather than intermetallic compounds or other complicated phases [1012]. Solid solutions
with multi-principal elements will tend to be more stable at
elevated temperatures because of their large mixing entropies
[20]. Therefore, it is believed that the oxide film having a simple
structure and a good thermal stability is relevant to high-entropy
effect. In order to further confirm the phase of the oxide films,
TEM was employed to analyze the films. The results of typical
oxide film deposited under CO2 = 30% are shown in detail. The
TEM morphology of the oxide film is shown in Fig. 5. Inset is
the corresponding electron diffraction patterns (EDP). Similar to
XRD result, TEM analysis also indicates the oxide film is HCP.
3.2. SEM analysis
Figs. 68 show the SEM morphology of the sputtered oxide
films of AlCoCrCu0.5 NiFe high-entropy alloy. It is observed
that the oxide film is composed of nanograin. Before annealing,
the grain size is about 30 nm at CO2 = 10 and 50% as shown in
Figs. 6(a) and 8(a). When the oxygen content is CO2 = 30%,
there are two kinds of particles with different sizes as shown in
Fig. 7(a). The smaller is 40 nm in size and the bigger between
70 and 150 nm. From Figs. 68, the grain size increases with
the anneal temperature and the micro-holes among gains are

apparently enlarged during annealing. This is due to the fact


that grains grow up during annealing and the number of grains
decreases. The piling of bigger grains results in bigger microhole formation. It is also seen that the surface roughness of film
tends to increase with the anneal temperature. This is also related
with the piling of bigger grains.
The chemical compositions of the sputtered alloy film or
oxide films of AlCoCrCu0.5 NiFe high-entropy alloy were analyzed using EDS. The results are shown in Table 1. It is seen
that the oxygen concentration of the oxide film increases with
the oxygen content (CO2 ) in the working gas. After annealing,
the films deposited under CO2 = 10 and 30% tend to absorb oxygen and cause the oxygen concentration of film to increase. This
is reasonable since, although anneal was carried out on a vacuum furnace, there still existed oxygen in the anneal furnace.
However, the oxygen concentration of the oxide film deposited
under CO2 = 50% changes very little during annealing, indicating oxygen is saturated.
3.3. Hardness analysis
Fig. 9 shows the hardness value of the sputtered oxide films
of AlCoCrCu0.5 NiFe high-entropy alloy. Before annealing, the
film deposited at CO2 = 30% has the highest hardness value

Fig. 7. SEM morphology of the oxide film deposited at CO2 = 30%: (a) before annealing, (b) annealed at 500 C, (c) annealed at 700 C, (d) annealed at 900 C.

Y.-S. Huang et al. / Materials Science and Engineering A 457 (2007) 7783

81

Fig. 8. SEM morphology of the oxide film deposited at CO2 = 50%: (a) before annealing, (b) annealed at 500 C, (c) annealed at 700 C, (d) annealed at 900 C.

ing temperature. After the 900 C annealing of the oxide films


deposited at CO2 = 10, 30 and 50%, their hardness difference
tends to decrease. Since there is no phase transformation during annealing as discussed in Section 3.1, it is believed that
the change of both the oxygen concentration and grain size
of oxide film determines the film-hardness change. After hightemperature annealing, the grain size of the oxide films becomes

while that deposited at CO2 = 10% has the smallest, indicating


there exists an optimal oxygen concentration of oxide film that
results in the highest hardness value. The optimal concentration in this paper is 38.5% as shown in Table 1. The hardness
value of the oxide film steps down when the annealing temperature increases. However, the hardness of film synthesized at
CO2 = 30% is reduced most quickly with increasing the anneal-

Table 1
Chemical composition of the sputtered alloy film or oxide film of AlCoCrCu0.5 NiFe high-entropy alloy in atomic percentage
Oxygen content in the sputtering gas

Anneal temperature ( C)

Al

Co

Cr

Cu

Ni

0
10
10
10
10
30
30
30
30
50
50
50
50

500
700
900

500
700
900

500
700
900

20.9
14.5
14.8
14.0
14.2
12.9
13.5
12.7
12.5
11.8
11.9
11.5
11.8

17.9
12.4
11.8
12.1
11.6
10.5
10.2
10.4
10.7
10.2
10.4
10.3
10.6

16.4
11.0
11.4
10.8
11.2
10.0
10.3
9.8
9.8
9.2
9.5
8.8
9.2

8.3
5.9
5.3
5.5
5.4
5.1
4.9
4.9
5.0
4.6
4.5
4.3
4.6

18.0
12.6
12.5
12.3
12.4
11.2
10.9
10.8
10.9
10.0
9.8
9.7
9.8

Fe
18.5
13.0
12.9
12.3
12.7
11.8
11.4
11.2
11.4
10.7
11.2
10.9
10.8

30.6
31.3
33.0
32.5
38.5
38.8
40.2
39.7
43.5
42.7
44.5
43.2

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Y.-S. Huang et al. / Materials Science and Engineering A 457 (2007) 7783

Fig. 9. Hardness vs. substrate temperature or annealing temperature of the sputtered oxide films of AlCoCrCu0.5 NiFe high-entropy alloy.

similar as shown in Figs. 68 and the oxygen concentration difference decreases as given in Table 1. Thus, after annealing, the
hardness difference of the oxide films decreases.
3.4. Resistivity analysis
Fig. 10 shows the resistivity of the sputtered oxide films
of AlCoCrCu0.5 NiFe high-entropy alloy. The resistivity of
the AlCoCrCu0.5 NiFe-alloy film is also measured, about
320  cm. As the oxygen content increases from CO2 =
0 to 10%, the resistivity has a large enhancement by 20 times.
After that the resistivity decreases with the oxygen content
(CO2 ). The resistivity of the oxide film is larger than that of
the AlCoCrCu0.5 NiFe-alloy film deposited at CO2 = 0. This is
reasonable since the alloy film is metallic although it is amorphous as shown in Fig. 1. The oxide film is similar to oxidation
type semiconductor. With the oxygen content increase, oxygen
in the oxide is surplus and metal vacancies increase. Thus, the
conductivity of the oxide film is dependent on metal vacancies.
Fig. 10 also provides the resistivity of the oxide films annealed
at different temperature. The resistivity of the oxide film tends to

Fig. 11. Thickness vs. substrate temperature or annealing temperature of the


sputtered oxide films of AlCoCrCu0.5 NiFe high-entropy alloy.

increase with the annealing temperature. Since the phase structure does not change with the annealing temperature, resistivity
change during annealing is mainly relevant to the grain size and
density of oxide films. From Figs. 68, when the annealing temperature steps up, grain size becomes similar but the micro-hole
size among grains is enlarged. The larger micro-hole size results
in lower density and larger resistivity.
3.5. Thickness analysis
The thickness of the sputtered oxide films of AlCoCrCu0.5 NiFe high-entropy alloy was measured using SEM. The results
are shown in Fig. 11. Before annealing, the film thickness
decreases with the oxygen content (CO2 ). This is reasonable
since with increasing CO2 , along with exhaust gas more metallic oxide is pumped out of deposition chamber. The tendency of
three curves of thickness versus annealing temperature is similar. After annealing at 500 C, the oxide-film thickness increases.
After that the thickness decreases with the anneal temperature as
shown in Fig. 11. However, the variation of the thickness value
is very little. In other words, the thickness is at the same level.
This is reasonable since the bigger micro-hole formation among
grains results in the thickness increase as shown in Figs. 68,
whereas a little part of oxide was sublimed and pumped out
during annealing.
4. Conclusions

Fig. 10. Resistivity vs. substrate temperature or annealing temperature of the


sputtered oxide films of AlCoCrCu0.5 NiFe high-entropy alloy.

The sputtered oxide films of AlCoCrCu0.5 NiFe high-entropy


alloy are of simple structure. With no oxygen addition to the
working gas, the AlCoCrCu0.5 NiFe high-entropy alloy film is
amorphous. When the oxygen content in the working gas is
between 10 and 50%, the sputtered oxide films are HCP with
lattice constants of a = 0.3583 nm and c = 0.4950 nm. Before
annealing, both the resistivity and thickness of the oxide film
decrease with increasing oxygen content and the hardness value
reaches maximum at 30% O2 . No new phases in the oxide films
form during annealing, indicating the oxide films are very stable

Y.-S. Huang et al. / Materials Science and Engineering A 457 (2007) 7783

at high temperature. However, the crystal grains tend to grow


up and the micro-hole size among grains increases with the
annealing temperature. The resistivity of the oxide film steps
up with annealing temperature, whereas the hardness value
decreases. The oxide-film thickness changes very little during
annealing.
Acknowledgements
The authors gratefully acknowledge the financial supports for
this research by the National Science Council of Taiwan under
grant no. NSC-91-2120-E-007-007, the Ministry of Economic
Affairs of Taiwan under grant no. 92-CE-17-A-08-S1-0003 and
the Guangdong Provincial Natural Science Foundation under
grant no. 04300026. We also thank Doctor Davison for critically
reading and editing the manuscript.
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