Materials Today Nano 15 (2021) 100130

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Materials Today Nano

j o u r n a l h o m e p a g e : h t t p s : / / w w w . e v i s e . c o m / p r o fi l e / # / M T N A N O / l o g i n

Tuning nanostructure and mechanical property of FeeCoeNieCreMn

high-entropy alloy thin films by substrate temperature
M. Hu a, Q.P. Cao a, *, X.D. Wang a, D.X. Zhang a, b, J.-Z. Jiang a, **
a
International Center for New-Structured Materials (ICNSM), State Key Laboratory of Silicon Materials, and School of Materials Science and Engineering,
Zhejiang University, Hangzhou, 310027, People's Republic of China
b
State Key Laboratory of Modern Optical Instrumentation, Zhejiang University, Hangzhou, 310027, People's Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: Improving the mechanical property of high-entropy alloys (HEAs) with face-centered cubic (fcc) struc-
Received 21 April 2021 ture is critical for their potential applications. In this study, the effects of substrate temperature, Tsub, on
Received in revised form nanometer-sized structure and mechanical property of fcc-structured FeeCoeNieCreMn HEA thin films
6 June 2021
prepared by magnetron sputtering were systematically investigated. All films grow in a nanocolumnar
Accepted 20 June 2021
Available online 27 June 2021
manner and display a single fcc-structured solid solution phase with (111) preferential orientation in
addition to the reduced amorphous phase fraction and increased average grain size with increasing Tsub.
The top-surface cauliflower-like hierarchical microstructure with some voided boundaries for 293 K-film
Keywords:
HEA thin films
gradually disappears with increasing Tsub up to 573 K. For higher Tsub (673 Ke773 K), the obvious grain
Nanocrystalline growth occurs with significantly increased column size and roughness. The variations in normal hard-
Nanocomposite ness, H, and Young's modulus, Es, obtained from nanoindentation tests on the surface of FeeCoeNieCr
In-situ tensile test eMn HEA thin films experienced a process of first increasing and then decreasing with Tsub, with a
maximum at Tsub ¼ 573 K. The former increase is due to enhanced interfacial adhesion and the later
decrease is ascribed to the weakened grain boundary strengthening caused by grain growth. The 573 K-
film with a nanocomposite structure including hybrid nanocrystalline and amorphous phase exhibits the
highest H (~10.0 GPa) and Es (~185.5 GPa) and is the strongest in terms of hardness among reported Fe
eCoeNieCreMn HEAs without post-treatment. In-situ micro-tensile tests alone the surface of FeeCoeNi
eCreMn HEA thin films uncovered the higher lateral yield strength (~1.1 GPa), fracture strength
(~1.4 GPa), and Young's modulus (~64.3 GPa) for 573 K-film than those of 293 K- and 773 K-films as well,
consistent with nanoindentation results. Anisotropic mechanical responses normal to and along the
surface were clearly found in FeeCoeNieCreMn HEA thin films, which are caused by the nanocolumnar
morphology and the weakened columnar boundaries adhesion compared to the column itself.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction unusual mechanical properties [5e8], and one of the well-known

In conventional metal alloys, one or two major components act
as the matrix material, and solute atoms with small amounts
strengthen alloys and hinder dislocation movement via changing
local stress field [1]. Recently, high-entropy alloys (HEAs) have
attracted numerous attention because of their uniqueness in alloy
design concept and microstructure [2,3], consisting of five or more
elements with equimolar or near-equimolar ratios and forming a
simple single solid-solution phase [4]. HEAs exhibit a variety of
* Corresponding author.
** Corresponding author.
E-mail addresses: caoqp@zju.edu.cn (Q.P. Cao), jiangjz@zju.edu.cn (J.-Z. Jiang).
and intensive-studied HEAs is FeeCoeNieCreMn Cantor alloy
with a single face-centered cubic (fcc) structure. The
FeeCoeNieCreMn HEA displays superior ductility of ~80% in ten-
sile elongation at room temperature, and even higher ductility of
~110% and strain-hardening rate at cryogenic temperature (77 K)
because of the formation of nanotwins caused by low stacking fault
energy and twin boundary energy (TBE), while many conventional
metal alloys show ductile-to-brittle transition with decreasing
temperature [3,9e11]. However, the yield strength of the
FeeCoeNieCreMn Cantor alloy is very low, only about 400 MPa
[11e13]. Enhancing its strength becomes an urgent issue in the HEA
community.

https://doi.org/10.1016/j.mtnano.2021.100130
2588-8420/© 2021 Elsevier Ltd. All rights reserved.
M. Hu, Q.P. Cao, X.D. Wang et al.
Hence, tremendous efforts have been devoted to strengthening
FeeCoeNieCreMn HEA [3], for instance, refining grain size,
introducing nanotwins or stacking faults [14e16], forming sec-
ondary phase precipitates [17], adding small-sized interstitial atom
to solid solution phase [18e22]. Among them, reducing the grain
size to the nanocrystalline region has been generally considered as
an effective method to enhance the strength. Sun et al. [3] inves-
tigated FeeCoeNieCreMn alloy with various grain sizes ranging
from 88.9 mm to 0.5 mm processed by cold rolling and subsequent
annealing treatments. The yield strength increased from 230 MPa
to 888 MPa with decreasing grain size, concurring well with the
HallePetch relationship with the HallePetch coefficient, KHP, of
490 MPa mm1/2. Fu et al. [23] fabricated a bulk-sized fcc-structured
nanocrystalline Co25Ni25Fe25Al7.5Cu17.5 HEA with a grain size of
~95 nm by mechanical alloying followed by consolidation via spark
plasma sintering. Its compressive yield strength was measured to
be about 1,795 MPa, which is dramatically higher than the coarse-
grained Co25Ni25Fe25Al7.5Cu17.5 HEA (~192 MPa) with a grain size of
~397 mm. Besides the aforementioned strengthening methods, it
has been recently found that amorphization is another efficient
way to increase the strength [24]. For instance, Wu et al. [25] re-
ported a supra-nanometer-sized dual-phase glass-crystal thin films
with nanocrystalline cores embedded in amorphous glassy shells,
which exhibited a near-ideal strength higher than single glass and
nanocrystalline materials.
As one of the most common vapor deposition methods,
magnetron sputtering has a variety of adjustable parameters, which
provides the chance of manipulating phase structure, grain size and
distribution, and enables further improvement on the mechanical
property to meet the requirement of high-performance thin-film
materials. Meanwhile, the rapid cooling rate of vapor deposition
favors the formation of amorphous phase. Recently, some reports
have proved that the interfacial bonding between the nanocolumns
of vapor-deposited films can be improved by increasing substrate
temperature (Tsub), due to the enhanced atomic surface diffusion,
resulting in an increase in hardness [26]. With the prevailing trend
toward miniaturization and scalable integration in advanced
coating and microelectronics industries, designing and developing
strong materials with excellent strength and plasticity at micro/
nano scales is crucial for thin-film materials in micro-electro-
mechanical systems [27e29]. Here, a series of FeeCoeNieCreMn
HEA thin films were synthesized by magnetron sputtering with
various Tsub. We systematically investigated the effect of Tsub on the
microstructure and nanomechanical responses, and the underlying
mechanisms for Tsub-dependent structure and property have been
discussed.
2. Experimental procedures
2.1. Sample preparation
Iron, cobalt, nickel, chromium, and manganese pure metals
(>99.99 wt%) with the equal atomic ratio were used to fabricate the
FeeCoeNieCreMn HEA target by vacuum arc melting furnace and
vacuum casting machine. The FeeCoeNieCreMn HEA thin films
were deposited at various Tsub ranging from 293 K to 773 K on clear
(100)-Si wafers for 130 min in an ultra-high vacuum direct current
magnetron sputtering system (TA16-10D) with a base pressure of
2  106 Pa. The distance from the target to the substrate was
12 cm, the incident angle was 30 and deposition power was 90 W.
The deposition pressure, flow rate of Ar, and rotation speed of
substrate was kept at 0.3 Pa, 40 sccm, and 3 rpm, respectively. For
comparison, the bulk-sized FeeCoeNieCreMn HEA was prepared
by induction melting in a quartz tube and naturally cooled in a
vacuum. The 293 K- and 573 K-deposited FeeCoeNieCreMn HEA
2
Materials Today Nano 15 (2021) 100130
films were chosen to perform annealing treatments at both 473 K
and 673 K for 1 h inside the magnetron-sputtering chamber under a
vacuum of 8  106 Pa.
2.2. Microstructure characterization
The morphologies of top surface and cross-sectional fracture
surface, the thicknesses, and chemical compositions of the as-
deposited FeeCoeNieCreMn HEA thin films were characterized
by scanning electron microscopy (SEM, Zeiss Supra 55), equipped
with an energy dispersive X-ray spectrometer. The film thickness
was about 870e970 nm and determined from the fracture surface
SEM image. The compositional variations of the as-deposited films
and the alloy target were shown in Fig. 1, indicating that the
composition of the films deposited at various Tsub is quite similar to
the target composition with near-equimolar ratios. The crystal
structure of the thin film was determined by grazing incidence X-
ray diffractometer (XRD, RIGAKU D/MAX 2550/PU) with Cu Ka ra-
diation and the incidence angle of 1 at a scanning rate of 2 per
minute. The microstructure and the grain size of thin films were
characterized by transmission electron microscopy (TEM, FEI Tec-
nai G2 F20 STWIN). Cross-sectional TEM samples were fabricated
by focused ion beam (FIB, FEI Quanta 3D FEG) milling, and an
extremely low energy beam (2 kV and 8 pA) was used to perform
the final polishing process to minimize possible Ga contamination.
The surface morphology and roughness were studied by atomic
force microscopy (AFM, SPM-9700) in tapping mode with a scan
rate of 1 Hz and five different areas of 2  2 mm2 with a resolution of
256  256 pixels were selected for analysis. The root-mean-square
(RMS) roughness was calculated by the software of SPM-9700.
2.3. Nanomechanical tests
Nanoindentation tests were performed in Agilent Nano Indenter
G200 at room temperature to obtain the hardness and Young's
modulus of thin films with a three-sided pyramidal Berkovich
indenter at the strain rate of 0.05 s1. A maximum indentation
depth of 90 nm was set, less than 10% of the total film thickness to
avoid possible substrate effect on the obtained results. At least 20
different indentations were performed, and the average hardness
and Young's modulus values were calculated. Vicker microhardness
measurement for the prepared bulk-sized alloy was conducted
with an MH-50 apparatus at a load of 200 g and a dwell time of 15 s.
Fig. 1. The compositions of the as-deposited FeeCoeNieCreMn HEA thin films at
various Tsub.
M. Hu, Q.P. Cao, X.D. Wang et al.
Tensile samples with the aspect ratio (length/width in gauge
region) of 2e3 were fabricated by FIB and then transferred to a
push-to-pull (PTP) device [30]. In-situ tensile tests were conducted
inside the SEM chamber, using Hysitron PI85 SEM PicoIndenter
with a high resolution of ~0.4 mN and ~1 nm. All tensile tests were
performed on the PTP with nominal stiffness of 230 N/m at a strain
rate of 1  103 s1 under displacement control. In the tension
process, a video was recorded, from which one can preciously
measure the length change to calculate the elongation of the tensile
sample.
3. Results and discussion
3.1. Microstructure of thin films
Typical XRD patterns of FeeCoeNieCreMn HEA thin films
deposited at various Tsub are shown in Fig. 2. Only one broad
diffraction peak located at 2q z 43.7 is observed for 293 K-film,
which is in good agreement with the peak for (111) plane of fcc
phase in FeeCoeNieCreMn HEA [31,32]. The broadening of
diffraction peak may be attributed to the poor crystallinity of fcc
phase with a very small grain size (details are discussed by TEM
measurements). With Tsub increasing from 293 K to 673 K, the
diffraction peak gradually becomes sharp and strong, which is
generally due to the obvious grain growth and improved crystal-
linity caused by the enhanced atomic surface diffusivity during
vapor deposition. Meanwhile, all films exhibit only a (111)-fcc
diffraction peak, suggestive of an obviously preferred orientation.
However, for the highest-Tsub of 773 K film, the XRD spectrum
shows strong (111), weak (200), and (220) peaks located at
2q z 43.7, 51.0 , and 71.4 , respectively, indicative of a typical
single-phase fcc-structured solid solution, together with a weak-
ened preferred orientation [33]. It is evident that the microstruc-
ture of FeeCoeNieCreMn HEA thin film is Tsub-dependent, with
obvious (111)-preferred orientation of fcc phase during the film
growth.
Top surface SEM images of FeeCoeNieCreMn HEA thin films
deposited at various Tsub are displayed in Fig. 3(a)e(e). For the
293 K-film, a cauliflower-like hierarchical microstructure is
observed. Small granular particles with an average size of ~30 nm
serve as the building blocks and aggregate to form large agglom-
erates with an average size of ~90 nm. Another feature is the
presence of voided boundaries/nanocracks between some adjacent
large agglomerates [26,34]. This can be ascribed to the shadowing
effect from oblique incident angle, and limited surface diffusion of
Fig. 2. XRD patterns of FeeCoeNieCreMn HEA thin films deposited at various Tsub.
3
Materials Today Nano 15 (2021) 100130
adatoms at low-Tsub. With increasing Tsub to 473 K and 573 K, the
voided boundaries gradually disappear, and the feature of hierar-
chical microstructure becomes increasingly obscure. For 573 K-film,
the size of small granule remains almost unchanged within the
experimental error, as compared to 293 K-film and 473 K-film. As
Tsub rose to 673 K, a unique morphology with facet feature was
clearly seen, indicating an evident preferred-orientation grain
growth of fcc phase. The average particle size is estimated to be
about 100 nm. Further increasing Tsub to 773 K, the morphology
with facet growth disappeared and grain coarsening occurred with
a mean particle size of about 147 nm, consistent with the XRD
pattern without strong preferred orientation. It can be interpreted
from an energy perspective. According to Pelleg and Gao et al.
[35e37], the preferred orientation of the film is decided by the
lowest overall system energy conditions resulting from a critical
competition between the surface and strain energies. For fcc-
structured crystals, lower atomic mobility can favor the growing
of (111) plane due to the minimum surface energy since the (111)-
oriented plane has the most densely packed feature for fcc-
structured crystals. Meanwhile, grains generally grow via a strain
relief mechanism with the Tsub combined with a decreased (111)
peak which is provided with relative higher strain energy
compared with other peaks in fcc-structured crystals [38,39].
Therefore, the enhanced atomic diffusion and the increased Tsub of
773 K inhibits the (111) preferred orientation of the film probably
based on energy considerations. Furthermore, the cross-sectional
SEM images of fracture surface for FeeCoeNieCreMn HEA films
were shown in Fig. 3(f)e(j). It can be observed that thin films
deposited at Tsub ¼ 293 K, 473 K, and 573 K clearly grow in a
columnar manner, but the boundary feature between adjacent
nanocolumns becomes less obvious with increasing Tsub, which is in
line with the gradual disappearance of voided boundaries/nano-
cracks on top surfaces as shown in Fig. 3(a)e(c). With Tsub
increasing to 673 K and 773 K, the columnar characteristic is further
weakened, making the boundaries less recognizable during cleav-
age due to the enhanced interface bonding.
The two- and three-dimensional AFM images, together with the
statistical histograms of top-surface granular particle size of
FeeCoeNieCreMn HEA thin films deposited at different Tsub are
shown in Fig. 4. The average particle size deduced from AFM images
of all films as a function of Tsub in general accords with the SEM
observation. The three-dimensional top surface AFM images of the
FeeCoeNieCreMn HEA thin films show a variation in RMS
roughness, which increases from 3.0 to 4.6 nm for 293 K-573 K-
films to 12.0e14.1 nm for 673 K- and 773 K-films. Surface particle
size and RMS roughness remain almost unchanged for the films
deposited at low and medium Tsub (293 Ke573 K), whereas for
relatively high Tsub (673 K and 773 K), both films exhibit an
apparent increase in particle size and roughness due to grain
growth.
The microstructures of as-deposited FeeCoeNieCreMn HEA
thin films were studied by TEM. The cross-sectional TEM images of
293 K-, 573 K-, and 773 K-films are shown in Fig. 5(a), (d), and (g),
respectively. The columnar growth directions are indicated by
white arrows, and all films exhibit a nanocolumnar growth manner.
It is clear that in 293 K-film, the voided boundaries (wide bright
lines) can be seen, which gradually disappear with increasing Tsub
to 573 K and 773 K. The selected area electron diffraction patterns
reveal that all films have a single fcc solid solution phase, consistent
with XRD results, whereas the low-Tsub film contains a relatively
high fraction of amorphous phase as compared with high-Tsub film,
suggested by the increased number of diffraction spots and the
weakened halo diffraction ring signal with Tsub. For 293 K- and
573 K-films, the nanocolumnar width is estimated to be about
20e30 nm, whereas it increases to about 70e100 nm for 773 K-film
M. Hu, Q.P. Cao, X.D. Wang et al.
Fig. 3. Top-surface topography and cross-section morphology SEM images of FeeCoeNieCreMn HEA thin films deposited at different Tsub of (a, f) 293 K, (b, g) 473 K, (c, h) 573 K, (d,
i) 673 K, and (e, j) 773 K. The substrate Si and film are marked, respectively.
with not clearly visible columnar boundaries. Moreover, only small-
sized nanocrystals form in 293 K-film, and some large nanograins
for the 573 K-film can be seen besides these small-sized crystals, as
shown in Fig. 5(a) and (d). High-resolution TEM (HRTEM) image of
the 293 K-film is displayed in Fig. 5(b). Several nanograins with an
average size of about 5e10 nm embedded in amorphous matrix
were detected, suggestive of a poor crystallinity in line with the
relatively broadened diffraction peak. The inverse fast Fourier
4
Materials Today Nano 15 (2021) 100130
transforms (IFFT) image from the white rectangular box in Fig. 5(b),
as shown in Fig. 5(c), exhibit abundant dislocations in fcc phase,
which could be ascribed to internal stress due to low atomic surface
diffusion. Fig. 5(e) is the HRTEM image of the 573 K-film with red
dotted lines showing some small nanocrystals with an average
grain size of about 5e10 nm. In addition, several large grains with a
size much larger than 10 nm can be observed, and the white rect-
angular box in Fig. 5(e) marks the part of the large grain. Fig. 5(f) is
M. Hu, Q.P. Cao, X.D. Wang et al. Materials Today Nano 15 (2021) 100130

the IFFT image from the white rectangular box in Fig. 5(e), and the
crystalline interplanar spacing is measured to be about 0.21 nm
corresponding to the (111) crystal plane of fcc solid solution phase
[40]. As for 773 K-film, the grain growth is obvious, as seen in
Fig. 5(g), with an average grain size up to about 70e100 nm. The
HRTEM image of a large grain in 773 K-film is displayed in Fig. 5(h)
with clear crystal lattice fringes. Some nanotwins can be detected
from the IFFT image shown in Fig. 5(i), which can be ascribed to the
low stack fault energy (SFE) and TBE of the alloy [41]. The SFE
approximately equals twice the TBE, and is ~21 mJ/m2 for
FeeCoeNieCreMn HEA [25,30].
According to the aforementioned analyses on the evolution of
structure and morphology of deposited FeeCoeNieCreMn HEA
thin films with Tsub, here we try to discuss the growth mechanism
of deposited FeeCoeNieCreMn HEA thin films with an increase in
Tsub, as illustrated in Fig. 6. The adatoms during magnetron sput-
tering may diffuse over the surface of the substrate/film, and the
surface diffusivity depends on Tsub, that is, the higher Tsub, the larger
diffusion rate of the adatoms. At low Tsub, the deposited films here
display a cauliflower-like hierarchical microstructure with small
columns aggregating to form large agglomerates, and some voided
boundaries between the adjacent large agglomerate exist. This can
be attributed to the slow atomic surface diffusivity, which does not
overcome the shadowing effect caused by the inclined deposition
[26]. In the intermediate temperature range, atomic surface diffu-
sion is enhanced and the adatoms can diffuse into the shadowed
regions, leading to the gradual disappearance of voided boundaries,
and the feature of hierarchical microstructure becomes increas-
ingly obscure with Tsub. Note that the size of the building block unit
(nanocolumn) does not change within the experimental error as
compared with the low-Tsub deposited films, but the enhanced
crystallinity is clear and some large grains appear as shown in
Fig. 5(d) and (e). Further increasing Tsub to higher temperatures of
673 K and 773 K, the further enhanced atomic diffusion promotes
migration of different kinds of boundaries, such as grain bound-
aries, nanocolumn boundaries, voided boundaries, resulting in
particle coarsening and surface roughening, that is, obviously
increased surface particle size and nanocolumn width, RMS
roughness. A special facet growth feature at a high Tsub of 673 K is
clearly revealed, which is characteristic of the crystalline film.

3.2. Nanoindentation tests

To investigate the Tsub-dependent nanomechanical properties

including hardness H and Young's modulus Es of
FeeCoeNieCreMn HEA thin films, normal nanoindentation tests
along the columnar growth direction were performed on top sur-
face. The typical load-depth (P-h) curves of thin films deposited at
various Tsub are displayed in Fig. 7(a). At a maximum depth (hmax) of
about 90 nm, the maximum load (Pmax) of deposited thin films
gradually goes up with Tsub. The hardness is calculated according to
the OliverePharr formula [42] H ¼ Pmax 2
A , where A ¼ 24.3hp þ 616.6 hp
is the contact area between the indenter and specimens,
hp ¼ hmax  CPSmax is the contact depth after plastic deformation,
C ¼ 0.72 for the Berkovich indenter, and S is the contact stiffness at
Pmax calculated by the slope of initial 30% unloading curve. Here, S
pffiffiffi
can be expressed as S ¼ 2bpErffiffiffi A
p
, where b ¼ 1.034 for the Berkovich
Fig. 4. Two-dimensional and three-dimensional AFM images of FeeCoeNieCreMn indenter, Er is the reduced modulus [42,43]. The reduced modulus
HEA thin films deposited at different Tsub of (a, f) 293 K, (b, g) 473 K, (c, h) 573 K, (d, i) 1v2i 1v2s
673 K, and (e, j) 773 K. (inset: the upper-right images are statistics histograms of the
Er can be expressed as 1
Er ¼ Ei þ Es , where Es and ns are the
particle size distribution from two-dimensional AFM images). Young's modulus and Poisson's ratio of the specimen, Ei and ni are

5
M. Hu, Q.P. Cao, X.D. Wang et al. Materials Today Nano 15 (2021) 100130

Fig. 5. The cross-sectional TEM images of deposited FeeCoeNieCreMn HEA thin films. (a) TEM image with the corresponding selected area electron diffraction (SAED) pattern
shown in the inset, (b) HRTEM image, and (c) IFFT image stemmed from the white dashed rectangle in (b) showing lots of dislocations in the 293 K-film. (d) TEM image with the
corresponding SAED shown in the inset. (e) HRTEM image showing some nanograins marked by red dotted circles and (f) IFFT image originated from the white dashed rectangle in
(e) of the 573 K-film. (g) TEM image with the corresponding SAED shown in the inset, (h) HRTEM image and (f) IFFT image from the white dashed rectangle in (h) of the 773 K-film.
T, nanotwin.

Fig. 6. Schematic diagrams of the growth mechanism of deposited FeeCoeNieCreMn thin films with the increase in Tsub.

Fig. 7. (a) The nanoindentation P-h curves of FeeCoeNieCreMn HEA thin films deposited at different Tsub. (b) The calculated hardness, H, and Young's modulus, Es, as a function of
Tsub.

Young's modulus and Poisson's ratio of the diamond indenter, of the FeeCoeNieCreMn HEA thin films was set to be 0.264 ac-
respectively. For the diamond indenter, it has been reported that ni cording to Refs. [41,46]. The calculated normal H and Es are shown
and Ei are 0.07 and 1,141 GPa, respectively [44,45]. Furthermore, ns in Fig. 7(b). The variation of H and Es of the FeeCoeNieCreMn HEA

6
M. Hu, Q.P. Cao, X.D. Wang et al.
thin films with Tsub are almost identical, showing a tendency of first
increasing and then decreasing, and at the intermediate tempera-
ture of 573 K both values reach maximum. The 573 K-film shows
highest H and Es of ~10.0 GPa and 185.5 GPa, respectively. From
293 K to 573 K, both H and Es of FeeCoeNieCreMn HEA thin films
increase, which can be mainly ascribed to enhanced interfacial
adhesion, since the voided boundaries are largely eliminated for the
573 K-film as compared with 293 K-film. Further increasing Tsub
from 593 K to 773 K, both H and Es start to reduce. It is well-known
that high Tsub further eliminates the voided boundaries due to the
accelerated atomic surface diffusion, while it also facilitates grain
boundary migration resulting in obviously grain growth. As the
removal of voided boundaries generally strengthens the film, the
reduced H can be expressed as the weakened grain boundary
strengthening according to the HallePetch relationship [47,48],
caused by the obvious grain growth. It is well accepted that crystal
materials usually display obvious elastic anisotropy because of
different atomic arrangement and distance between atoms in
various crystal orientations or crystal planes. For fcc-structured
crystals, the largest Es corresponds to the growth direction along
the most densely packed (111) plane. Therefore, in comparison with
573 K-film, the weakened (111)-preferred orientation of the 773 K-
film results in a reduced Es. The ultimate relative lower Es for 773 K-
film indicates the reduction effect of Es caused by weakened (111)-
preferred orientation is over the corresponding enhancement effect
promoted by increased crystallinity. Vickers microhardness (154.3
HV, about 1.5 GPa) of the bulk-sized FeeCoeNieCreMn HEA with
average grain size of 37.4 mm, as shown in Fig. 8, prepared by in-
duction melting and naturally cooled, is used for comparison with
the hardness of deposited films. Comparison of hardness of
FeeCoeNieCreMn HEAs here and some reported references are
listed in Table 1 in detail. Note that all thin films are in the as-
Fig. 8. (a) XRD pattern with (111), (200), and (220) diffraction peaks located at 2q z 43.6 , 50.8 , and 74.7 and (b) back-scattered electron (BSE) SEM image of bulk-sized
FeeCoeNieCreMn HEA and (c) the corresponding statistical grain size showing the average grain size of 37.4 mm. (d) Vickers microhardness of as-prepared bulk
FeeCoeNieCreMn HEA.
7
Materials Today Nano 15 (2021) 100130
deposited state without any post-treatment. The 573 K-deposited
FeeCoeNieCreMn HEA thin film here exhibits the highest H
among the references. The superior properties of the 573 K-film can
be attributed to strong boundaries bonding between nanocolumns
and dual-phase nanocrystaleglass hybrid structure, also known as
nanocomposite, which was first discovered by Wu et al. to suc-
cessfully enhance strength of magnesium alloys (3.3 GPa), while
previously, for magnesium alloys, neither glass nor crystal excee-
ded 1.5 GPa in yield strength [25].
To investigate the reliability with the change of temperatures,
we performed annealing treatments for 293 K- and 573 K-depos-
ited FeeCoeNieCreMn HEA films. The microstructure is shown in
Figs. S1eS3 of SM, and Fig. S4 is corresponding nanoindentation
behavior with typical load-depth (P-h) curves of both films before
and after annealing treatment, in addition to the calculated hard-
ness, H, and Young's modulus, Es. Specific data are listed in Table S1
of SM. Obviously, both H and Es are slightly enhanced from the as-
deposited to 473 K-annealed and further to 673 K-annealed. It can
be mainly ascribed to the enhanced interfacial adhesion and
slightly increased crystalline fraction. Overall, both films demon-
strate good thermal stability and mechanical reliability with the
change of temperature.
3.3. In-situ microtensile tests
To further prove the above analyses of boundary adhesion, in-
situ microtensile tests were performed on 293 K-, 573 K-, and 773 K-
films at room temperature with the applied force perpendicular to
the column growth direction. The procedures for preparing the
free-standing film tensile samples are shown in Fig. 9(a). The ulti-
mate dog-bone-shaped tensile samples were fabricated by FIB with
a three-step fabricating method: 5 nA Ga ion beam for preliminary
M. Hu, Q.P. Cao, X.D. Wang et al.
Table 1
Comparison of the hardness of FeeCoeNieCreMn HEAs from the below reported references and this work (films and bulk alloy). All listed FeeCoeNieCreMn alloys and films
show homogeneous element distribution, moreover all listed FeeCoeNieCreMn HEA films are without post-treatment and specific substrate temperatures are indicated.
Materials Phase structure
NT Fe20.6Co18.6Ni16.2Cr23.1Mn21.5 film (293 K), Wang et al. [59] fcc
Fe20.6Co18.4Ni16.1Cr23.1Mn21.8 film (293 K), Wang et al. [59] amorphous
Fe19.1Co19.3Ni19.1Cr19.9Mn22.6 film (293 K), Dang et al. [60] fcc þ bcc
Fe20.0Co20.0Ni20.0Cr20.0Mn20.0 HEA, Lee et al. [61] fcc
Fe20.0Co20.0Ni20.0Cr20.0Mn20.0 HEA, Lee et al. [61] fcc
Fe21.0Co20.0Ni21.0Cr19.5Mn18.5 alloy, Schuh et al. [20] fcc
Fe20.4Co20.1Ni19.3Cr20.9Mn19.4 alloy, Heczel et al. [62] fcc
Fe20.4Co20.1Ni19.3Cr20.9Mn19.4 alloy, Heczel et al. [62] fcc
Fe20.0Co20.0Ni20.0Cr20.0Mn20.0 film (293 K), Xiao et al. [29] fcc
Fe20.0Co20.0Ni20.0Cr20.0Mn20.0 alloy, Shahmir et al. [19] fcc
Fe20.0Co20.0Ni20.0Cr20.0Mn20.0 alloy, Liu et al. [63] fcc
Fe20.0Co20.0Ni20.0Cr20.0Mn20.0 alloy, Liu et al. [63] fcc
Fe19.9Co20.9Ni21.3Cr18.5Mn19.4 film (293 K), this work fcc
Fe20.0Co21.4Ni21.6Cr18.3Mn18.7 film (573 K), this work fcc
Fe20.8Co20.7Ni21.6Cr18.4Mn18.5 film (773 K), this work fcc
Fe20.0Co21.0Ni21.8Cr18.3Mn18.9 alloy, this work fcc
NT, nanotwined.
fabrication of Pt-film-Si trilaminar cuboid, 1 nA Ga ion beam for fine
milling the trilaminar cuboid to be about 1,200 ± 100 nm in
thickness, and rotating the sample by 90 and using 50 pA Ga ion
beam for the final milling of bilateral Si and Pt to obtain a dog-bone-
shaped tensile samples with a gauge size of ~2,300 nm in length,
600 ± 70 nm in width, and 1,200 ± 100 nm in thickness. Note that
before the tensile sample fabrication, the Pt layer needs to be
sprayed on the film top surface with a thickness of ~2 mm as a
protective layer. The uniaxial quasi-static tensile tests were con-
ducted on a silicon spring PTP device where a flat indenter was
used to press the bump at the top of the device with displacement
control, and then the device will convert the compressive force into
the pulling force applied to the sample, as shown in Fig. 9(b)e(d).
Fig. 9(e) displays the raw load-displacement curves of 293 K-,
573 K-, and 773 K-films on the PTP device with black arrows rep-
resenting the fractured moment during the microtensile test, and
the continuous loading after fracture is needed to calculate the
stiffness of the empty PTP spring device. The actual force on the
sample can be expressed by the following equation [30]:
Fsample ¼ Fraw  kl (1)
where Fsample is the actual load force on the tensile sample, Fraw is
the applied force of indenter on PTP, k is the stiffness of the PTP
device (~230 N/m), and l represents raw displacement moved by
the indenter. The entire tension processes of 293 K-, 573 K-, and
773 K-films on the PTP device were recorded in movies (see in
Supplementary Movies 1e3 of SM), and video capture of the SEM
signal permitted correlation of mechanical testing results with the
snapshot images.
After correcting the displacement data with snapshots of in-situ
recorded video, typical engineering stressestrain (seε) curves for
the 293 K-, 573 K-, and 773 K-films and the lateral (parallel to film
surface) mechanical properties extracted from the stressestrain
curves including Young's modulus (E), yield strength (sy) and
strain (εy), fracture strength (sf) and strain (εf) are shown in Fig. 9(f).
Snapshots obtained from the recorded video of 293 K-film during
in-situ tensile test are shown in Fig. 9(g)e(d), while those of 573 K-
film and 773 K-film in Fig. 9(j)e(l) and Fig. 9(m)e(o), respectively.
Three SEM images for each film correspond to different strain
stages, that is, before tensile test, before fracture, and after fracture.
The elongation of the tensile samples was measured by length
change marked by two red lines. The 293 K-film exhibits a uniform
strain of about 1% before fracture, while there are 2.3% and 2.7% for
8
Materials Today Nano 15 (2021) 100130
Grain size (nm) Hardness (GPa)
~20 ~8.5
e ~9.6
~10 6.8
~40  103 2.0
~38 6.1
~50 5.1
~30 5.4
~60  103 1.4
3.8 8.9
10 4.4
8.4  103 1.5
3.9  103 1.6
5e10 5.0
10e20 10.0
70e100 6.0
~37.4  103 1.5
573 K- and 773 K-film, respectively. Meanwhile, the 573 K- and
773 K-films experience a small tensile plastic strain, εp, of 0.1% and
0.2% after yielding, respectively, but the 293 K-film exhibited a fully
brittle fracture with εp ¼ 0%. Therefore, the total elastic strain, εe, is
1.0% for 293 K-film, 2.2% for 573 K-film, and 2.5% for 773 K-film. The
yield strength, sy, acquired from the endpoint of the linear fitting to
the stressestrain curve and the fracture strength, sf, were deter-
mined to be 0.3 GPa (sy ¼ sf) for 293 K-film, 1.1 GPa and 1.4 GPa for
573 K-film, and 0.7 GPa and 1.1 GPa for 773 K-film. Obviously, the
573 K-film exhibits the highest strength (both sy and sf), consistent
with the nanoindentation results. Specimen size dependence in
strength has been widely reported in some small-scaled metallic
materials in microtensile tests, which also indicates the existence of
a strengthening effect on decreasing specimen size [49e51].
Therefore, the fabricated larger width of 573 K-film in comparison
with 293 K-and 773 K-film weakens its strength to some extent
according to ‘the smaller is stronger’ theory, suggestive of an
enhanced strength for 573 K-film if decreasing the width similar to
other two films. The yield strain, εy, was determined to be 1.8% and
1.6% for 573 K-film and 773 K-film, respectively, whereas for 293 K-
film, no yield appears. Comparing εe with εy for both 573 K- and
773 K-films, we observe that after yielding, there exist non-linear
elastic strains of 0.4% (¼2.2%e1.8%) and 0.9% (¼2.5%e1.6%) for
573 K- and 773 K-films, respectively. The value of E acquired from
the linear slope on the stressestrain curve was determined to be
~33.1 GPa for 293 K-film, ~64.3 GPa for 573 K-film, and ~45.7 GPa for
773 K-film, respectively. The relatively higher E for 573 K-film can
be ascribed to the elimination of abundant voided boundaries and
enhanced interfacial adhesion as compared with 293 K-film,
whereas the decrease in E from 573 K-film to 773 K-film could not
be determined by boundary bonding, because atomic surface
diffusion increases with Tsub. Meanwhile, the enhanced crystallinity
with a large grain size in 773 K-film as compared with 573 K-film
will increase the value of E in general due to a higher modulus of
crystalline phase in comparison with amorphous phase counter-
part. Therefore, another important factor, the internal thermal
stress, needs to be considered, especially at high Tsub. When
deposited at high Tsub, both FeeCoeNieCreMn HEA thin film and Si
substrate will undergo a cooling process, during which owing to the
difference in thermal expansion coefficient between the metallic
film and Si substrate [52e54], the metallic film with relatively
larger thermal expansion coefficient will shrink more and end up
with residual tensile stress perpendicular to the growth direction
due to the constraint from Si substrate. Numerous reports have
M. Hu, Q.P. Cao, X.D. Wang et al. Materials Today Nano 15 (2021) 100130

Fig. 9. Microtensile tests of 293 K-, 573 K-, and 773 K-films. (a) Schematic representation of the FIB procedures for preparing the film tensile sample. (b)e(c) PTP device depicting
how to load a representative FeeCoeNieCreMn HEA thin-film microtensile specimen. (d) SEM image shows the thickness of the microtensile sample. (e) The load-displacement
curve of HEA films on PTP device. During the microtensile test, the film samples are loaded until the sample fractures at certain displacements indicated by black arrows, and the
device is further loaded after fracture to calculate the stiffness of the empty PTP spring device. (f) Representative engineering stressestrain curves after correction and the me-
chanical properties extracted from the stressestrain curves include Young’ s modulus (E), yield strength (sy) and strain (εy), fracture strength (sf) and strain (εf). (g)e(i) Images of
the free-standing tensile 293 K-film samples at various strain stages, (j)e(l) and (m)e(o) correspond to 573 K-film and 773 K-film, respectively. All the scale bars indicate a length of
400 nm.

shown that the residual tensile stress is prone to promote the for-
mation of cracks thus leading to deteriorated mechanical proper-
ties, such as strength, hardness, interface adhesion strength, fatigue
strength, and so on. [55e58]. The existence of residual tensile stress
would reduce the mechanical strength and modulus of thin film
deposited at high Tsub. Comparing the lateral yield strength and the
Young's modulus from tensile test with normal hardness and
Young's modulus from nanoindentation test, we clearly see aniso-
tropic mechanical response in FeeCoeNieCreMn HEA thin films
with nanocolumnar structure. The lateral E obtained from the
tensile test was mainly determined by the bonding strength of
columnar boundaries, whereas the normal Es from nano-
indentation test was mainly controlled by columns themselves
because of the low boundary fraction underneath the indenter.
Such anisotropic mechanical response suggests the weak bonding
of columnar boundaries compared to nanocolumn itself.
4. Conclusions
In this work, typical FeeCoeNieCreMn HEA thin films with
various nanostructure and mechanical properties were fabricated
by magnetron sputter under various Tsub. Microstructure and
nanomechanical properties (including nanoindentation normal to
the surface and in-situ microtensile tests along the surface) of
newly prepared HEA films were systematically studied. Our results
allow the following conclusions to be drawn:
All films grow in a nanocolumnar manner, exhibiting a single fcc
solid solution phase with (111) preferential orientation, and the
amorphous phase fraction increases with decreasing Tsub. At low
Tsub of 293 K, cauliflower-like hierarchical microstructure is formed,
and the voided boundaries gradually disappear with increasing Tsub
up to 573 K. Surface particle size and RMS roughness remain almost
unchanged, and some large grains appear due to the enhanced

9
M. Hu, Q.P. Cao, X.D. Wang et al.
atomic surface diffusivity and grain boundary migration. For high
Tsub (673 Ke773 K), both column size and roughness rise signifi-
cantly, and the obvious grain growth occurs.
The variations in normal H and Es obtained from nano-
indentation tests of FeeCoeNieCreMn HEA thin films experienced
a process of first increasing and then decreasing with Tsub, with a
maximum at Tsub ¼ 573 K. The former increase is due to enhanced
interfacial adhesion, since the voided boundaries are largely elim-
inated for the 573 K-film as compared with 293 K- and 473 K-films,
and the later decrease is ascribed to grain growth, which can be
expressed as the weakened grain boundary strengthening due to
increased grain size. The 573 K-film with a nanocomposite struc-
ture including hybrid nanocrystalline and amorphous phase ex-
hibits the highest H (~10.0 GPa) and Es (~185.5 GPa) and is the
strongest in terms of hardness among reported FeeCoeNieCreMn
HEAs without post-treatment.
In-situ microtensile tests were used to characterize the lateral
tensile behaviors and the boundaries adhesion of 293 K-, 573 K-,
and 773 K-films. The 573 K-film shows higher yield strength
(~1.1 GPa), fracture strength (~1.4 GPa), and Young's modulus
(~64.3 GPa) than 293 K- and 773 K-films, consistent with nano-
indentation results. All films exhibit poor plasticity (0e0.2%) due to
special columnar structure. Moreover, by comparing the hardness
and Young's modulus from normal nanoindentation tests with
strength and Young's modulus from lateral tensile tests, anisotropic
mechanical response was clearly found in FeeCoeNieCreMn HEA
thin films with nanocolumnar structure, indicative of the relatively
weak nanocolumnar boundary adhesion compared with the
nanocolumn itself.
CRediT authorship contribution statement
M. Hu: Investigation, Writing e original draft, Software. Q.P.
Cao: Conceptualization, Methodology, Data curation, Writing e
review & editing, Supervision, Project administration, Funding
acquisition. X.D. Wang: Resources. D.X. Zhang: Resources. J.-Z.
Jiang: Supervision, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
Financial supports from the National Natural Science Foun-
dation of China (51871198, U1832203, and 11975202), the Na-
tional Key Research and Development Program of China
(2017YFA0403400), and the Fundamental Research Funds for the
Central Universities are gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.mtnano.2021.100130.
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