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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
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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%.
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.
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
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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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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
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
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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.
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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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
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
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