Materials Today Advances 8 (2020) 100114

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Materials Today Advances

journal homepage: www.journals.elsevier.com/materials-today-advances/

Design and synthesis of chemically complex ceramics from the

perspective of entropy
J. Liu a, *, G. Shao b, D. Liu c, K. Chen d, K. Wang e, B. Ma e, K. Ren f, Y. Wang f, **
a
State Key Laboratory of Traction Power & School of Mechanics and Engineering, Southwest Jiaotong University, Chengdu, Sichuan 610031, China
b
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou, Henan 450001, China
c
School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu, Sichuan 610031, China
d
School of Energy, Power and Mechanical Engineering, North China Electric Power University, Beijing, 102206, China
e
School of Mechanical Engineering, Dongguan University of Technology, Dongguan, Guangdong, 523808, China
f
Institute of Advanced Structure Technology, Beijing Institute of Technology, Haidian District, Beijing, 100081, China

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

Article history: High-entropy ceramics (HECs) have rapidly expanded from high-entropy oxides to high-entropy ultra-
Received 20 June 2020 high temperature ceramics/coatings and have drawn extensive attention in the field of ceramics. In
Received in revised form addition, high-entropy thermoelectric materials focus on the topic of energy, which is another major
7 August 2020
driving force to accelerate the development of HECs. In this review, the recent progress on the design and
Accepted 24 August 2020
Available online 14 October 2020
synthesis of chemically complex ceramics is summarized. The fundamental understanding of configu-
rational entropy, phase stability, and formation criterion of HECs are discussed. Critical comments on the
compositionally complex ceramics and mixed-valence complex ceramics are presented. The synthesis
Keywords:
High-entropy ceramics
methods of HECs are summarized, and reactive flash sintering is highlighted as a new strategy to syn-
Configurational entropy thesize HECs. The new design ideas and synthesis methods can provide more opportunities to develop
Multicomponent high-performance HECs to meet the requirements of cutting-edge applications.
Oxides © 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
Aliovalent cation license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Flash sintering

1. Introduction
Multicomponent ceramics have been investigated widely in the
ceramic community, such as electronic ceramics [1], coatings [2],
glass [3], and so on. However, the amount of dopant or additive in
multicomponent ceramics is very low compared with the principal
component, and the traditional multicomponent ceramics usually
have complex phase structure. In 2004, high-entropy alloys (HEAs)
as new materials were developed by Yeh et al. [4] and Cantor et al.
[5] using five or more equimolar elements. Then, the idea of HEAs
was combined with ceramic to develop high-entropy nitride and
oxide films with excellent mechanical properties at very early stage
[6,7]. However, high-entropy ceramics (HECs) did not attract
extensive attention until Rost et al. [8] in 2015 prepared entropy
stabilized oxides (ESOs) with high configurational entropy, which
are (Mg, Co, Ni, Cu, Zn)O ceramics with single rock salt phase
* Corresponding author.
** Corresponding author.
E-mail addresses: liujinling@swjtu.edu.cn (J. Liu), wangyiguang@bit.edu.cn
(Y. Wang).
(Fig. 1). Owing to their good functional characteristics, such as en-
ergy storage [9e15], catalytic activity [16e18], low thermal con-
ductivity [19,20], dielectric properties [21], and magnetic
properties [22e24], ESOs have stimulated interest in the ceramics
community. Recently, ESOs have expanded to include fluorite
[25e32], perovskite [33e40], spinel [41e46], magnetoplumbite
[47e49], bixbyite [50], and amorphous structure [51,52].
Gild et al. [53] first extended the scope of HECs to include high-
entropy metal diborides with hexagonal AlB2 structure in 2016.
Since then, high-entropy borides [54e68], carbides [69e97], sili-
cides [98e100], zirconates [101e107], silicates [108e110], phos-
phates [111,112], and niobates [113] have been investigated widely.
These materials exhibit excellent thermophysical and mechanical
properties, such as low thermal conductivity, matched thermal
expansion coefficient, good thermal stability, high strength, and
ultrahigh hardness. Therefore, they have become a new class of
candidate materials for thermostructure, thermoprotection, ther-
mal barrier coating, and environmental barrier coating
applications.
Moreover, HECs with single-phase crystalline structure and
distorted lattice can induce the scattering of phonons and good

https://doi.org/10.1016/j.mtadv.2020.100114
2590-0498/© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/
).
J. Liu, G. Shao, D. Liu et al.
electronic conductivity. Hence, they have been considered for
designing high-performance thermoelectric materials recently
[114e116]. To date, high-entropy ultrahigh temperature ceramics/
coatings have attracted significant attention in the ceramic
community.
The development status of HECs has been reviewed compre-
hensively in several recent reports [117e119]. Here, the advances in
design concepts for HECs are reviewed first, and then composi-
tionally complex ceramics (CCCs) and mixed-valence complex ce-
ramics (MVCCs) are discussed. After a brief review of the common
synthesis methods for HECs, reactive flash sintering is presented as
a new route to produce HECs via fast solid-state reaction based on
the lattice defects and ‘softening of lattice’ under electric field. This
strategy can provide the possibility to increase atomic solubility
and lattice tolerance in HECs.
2. Entropy-driven design of multicomponent ceramics
2.1. Ideal configurational entropy of multicomponent ceramics
HEAs are defined based on their composition, entropy, single-
phase solid solution microstructure, and other combined defini-
tions [4,5,120e124], which is still an open question in this field.
Generally, entropy sources comprises contributions from configu-
ration, vibration, electronic excitation, and magnetism; however,
the configurational entropy has a significant effect on the HEAs. In
an ideal solid solution, the ideal configurational entropy (also called
mixing entropy) of mixing per mole can be calculated using the
following equation [123]:
X
N
DSmix ¼  R xi lnxi
i1
where R is the gas constant, xi is the molar fraction of the ith
element, and N is the total number of the constituent elements.
Consequently, the maximum ideal configurational entropy is
reached for an equiatomic HEA, which is given by the following
equation [123]:
DSmix ¼  RlnðNÞ
Generally, alloys with DSmix >1.61 R are classified as HEAs, alloys
with 0.69R < DSmix < 1.61 R are classified as medium-entropy al-
loys, and alloys with DSmix < 0.69 R are classified as low-entropy
alloys [121]. Other scholars have proposed that HEAs have DSconf 
1.5R per mole, which has become a more popular classification
method now [125].
In 2015, Rost et al. [8] extended the entropy concept of HEAs to
bulk five-component oxide ceramics. Different from the simple
crystalline structure of metals, ceramics possess complex crystal-
line structure. For example, rock salt oxides have cation and anion
sites in the lattice. Generally, the cations and anions occupy
different sublattice and/or interstitial sites in ceramics, and they
only mix in the individual sites. Hence, the ideal configurational
entropy in the ceramic systems is given by [118]:
h X
N  X
L 
DSmix ¼  R xi lnxi þ xj lnxj
Cationsite
i1 j1
where xi and xj represent the mole fraction of elements present in
the cation and anion sites, respectively. In addition, if there are two
cation sublattices in the ceramics, such as perovskite, spinel,
pyrochlore oxides, and so on, two parts of ideal configurational
entropy from cation sublattices with similar expression should be
Materials Today Advances 8 (2020) 100114
included to describe the ideal configurational entropy [34]. The
equation is as follows:
h X
M  X
N 
DSmix ¼ R xh lnxh þ xi lnxi
Asite Bsite
h1 i1
(4)
X
L  i
þ xj lnxj
j1
Anionsite
where xh and xi represent the mole fraction of elements present in
the A and B cation sites, respectively. It should be noted that the
configurational entropy from interactions of sublattices in ceramics
has been ignored in Eqs. (3) and (4), and the number of atoms in
different sublattices has not been considered when combining the
cation sites and anion sites together, which should underestimate
the ideal configurational entropy of ceramics with complex crys-
talline structure.
Eq. (4) imply that the maximum ideal configurational entropy
will be increased significantly compared with the ceramics with
only one cation sublattice. Hence, large ideal configurational en-
tropy can be reached in the ceramics with complex crystalline
structure, which would benefit the entropy stabilization in ceramic
system. Jiang et al. successfully synthesized homogenous single-
phase high-entropy ABO3 perovskite oxides with composition of
(Sr0.5Ba0.5) (Zr0.2Sn0.2Ti0.2Hf0.2Nb0.2)O3, where both A-site and B-
site were populated with different elements in equiatomic amounts
[33]. Zhao et al. reported the preparation of single-phase high-
entropy ceramic (Y0.25Yb0.25Er0.25Lu0.25)2(Zr0.5Hf0.5)2O7 with
defective fluorite structure [105]. Recently, Wright et al. systemat-
ically varied mass and size disorder on both A and B sublattices of
A2B2O7 pyrochlores [107]. A similar strategy was also used for
(1) obtaining spinel structure by Parida et al. [45] and magneto-
plumbite structure by Vinnik et al. [49]. Besides the cation site,
anion site with different elements will induce high entropy in the
multicomponent ceramic system. Wang et al. [12] synthesized a Li-
containing entropy stabilized oxyfluoride using multi-anionic and
multicationic sites. Recently, Li et al. [126] obtained a single-phase
Ti1/2Zr1/2(C1/3N1/3O1/3) solid solution with rock salt structure at
2,000  C using mixed ZrO2, ZrN, ZrC, TiO2, TiN, and TiC powders
with equiatomic anions. Wen et al. [127] also reported a high-en-
(2) tropy alumino-silicide (Mo0.25Nb0.25Ta0.25V0.25) (Al0.5Si0.5)2 with
multicationic and multi-anionic structure. Multicomponent ther-
moelectric material systems with mixing anion can be obtained by
the same strategy [114,128,129]. Moreover, the non-stoichiometric
ratio of the anion sublattice also contributes to the additional
configurational entropy in multicomponent ceramics, but the
increment is small [15e18,26,28,31,36,37,43,130e132]. Indeed, the
real configurational entropy in multicomponent ceramics is
significantly different from the ideal configurational entropy,
particularly at a low temperature with solid state [124,133].
2.2. Entropy stabilization and phase stability
Rost et al. [8] demonstrated that the entropy-driven trans-
formation of (Mg, Co, Ni, Cu, Zn)O ceramic to single-phase rock salt
i occurs between 850 and 900  C from mixed rock salt and tenorite
(3) phase (Fig. 2). The reversible entropy-driven phase transformation
Anionsite
was also investigated carefully by Dupuy et al. [134], Hong et al.
[135], and Bhaskar et al. [132]. Chen et al. [27] first demonstrated
that (Ce0.2Zr0.2Hf0.2Sn0.2Ti0.2)O2 ceramic is entropy stabilized oxide
based on the reversible transition between the low-temperature
multiphase and high-temperature single-phase fluorite structure.
The entropy-driven structural stabilization of the perovskite type
(Gd0.2La0.2Nd0.2Sm0.2Y0.2)MnO3 system was also revealed by Sarkar
2
J. Liu, G. Shao, D. Liu et al.
Fig. 1. (a) X-ray diffraction analysis of (Mg, Co, Ni, Cu, Zn)O (labeled as J14) with single rock salt structure, and carrots identify peaks from other crystal structures when individual
components are removed from the (Mg, Co, Ni, Cu, Zn)O solid solution. (b) Calculated configurational entropy in an N-component solid solutions as a function of mol% of the Nth
component. (a) and (b) adapted from a study by Rost et al. [8] CC-BY-4.0 (https://creativecommons.org/licenses/by/4.0/).
et al. [34]. Regarding high-entropy ultrahigh temperature ceramics,
Harrington et al. [77] reported that (V0.2Nb0.2Ta0.2Mo0.2W0.2)C is
likely an entropy stabilized carbide.
It should be noted that the phase stability not only depends on
the ideal configurational entropy but is also affected by the tem-
perature and enthalpy. According to the Gibbs free energy:
DGmix ¼ DHmix  T DSmix
where DGmix and DHmix are the mixing free energy and enthalpy,
respectively, and T is the absolute temperature. Hence, reversible
phase transformation can be observed with the change in tem-
perature of entropy stabilized ceramics. However, enthalpy also
affects the phase formation and stability. For example, the enthalpy
of mixing is significantly increased when Ca is substituted into the
(Co, Cu, Mg, Ni, Zn)O lattice instead of Mg, which leads to an
extremely high temperature requirement for stabilizing the single-
phase rock salt structure [133]. Djenadic et al. [25] and Pianassola
et al. [30] suggest that not only the entropy effect but also the type
of elements, synthesis procedure, and crystallite size should be
considered as factors for structural stabilization. The effect of
composition on the crystalline structure has been investigated
widely in high-entropy fluorite oxides [28,31], perovskite oxides
[33,34], pyrochlore oxides [101,107], borides [53,57e59], as well as
in carbides [73,77]. It was found that the HECs with stable single-
phase structure cannot be predicted very well by considering only
the ideal configurational entropy.
2.3. Formation criterion of HECs
Although the formability of single-phase HECs can be evaluated
using Gibbs free energy from first-principles calculations
[54,63,67,71,74,76,127,133], the use of descriptors is a more com-
mon method to discover and design new HECs similar to the HEAs.
Based on the Hume-Rothery rules for the formation of random solid
solution, several descriptors have been proposed to predict HEAs,
but the atomic size effect (d) and the enthalpy of mixing (DHmix) are
Materials Today Advances 8 (2020) 100114
the two main criteria [122e124]. They have also been widely used
to evaluate the formation of HECs. As the enthalpy of mixing is
difficult to achieve in high-entropy ceramic system, and the mixing
enthalpy of HECs is relatively low, the atomic size effect (d) has been
proposed as the primary criterion [40,53,54,74,76,82,85,127,136].
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u
(5) uXN h . X N i2
d ¼ t i¼1 xi 1  r xi r i (6)
i¼1
where ri and xi are the atomic radius and molar content of the i-th
component. Especially, the tolerance factor (t), which was proposed
by Goldschmidt, has been used to predict the stability of single
high-entropy perovskite phase with two A and B cation sublattices
[33,34].
R þ RO
t ¼ pffiffiffi A (7)
2ðRB þ RO Þ
The aforementioned equation suggests that a Goldschmidt
tolerance factor close to 1 is an important criterion for the forma-
tion of single high-entropy perovskite phase.
Generally, the atomic size effect (d) and/or Goldschmidt toler-
ance factor (t) is a necessary, but not sufficient, criterion to predict
the formation of single HEC. The factors such as composition,
crystalline structure, mixing enthalpy, valence electron concen-
tration (VEC), and so on are not negligible. Hence, several new
descriptors have been proposed to predict the formation of HECs
[67,73,114]. Liu et al. [114] used d as a criterion for evaluating the
atomic solubility in a two-component semiconducting solid
solution.
GR* ðDR* Þ2
d¼ (8)
Z
where G is the average shear modulus, R* is the effective lattice
constant, and Z is the number of formula units in a unit cell.
3
J. Liu, G. Shao, D. Liu et al. Materials Today Advances 8 (2020) 100114

Table 1
The typical synthesis routes of high-entropy ceramics.

Types Methods Advantages Disadvantages References

Powder Wet chemical Flame spray Short processing time Very short 140e141
methods pyrolysis Very fine crystalline size residence time
Nebulized spray High production rate High temperature 25, 34, 141-142
pyrolysis Nanocrystalline
Co-precipitation The crystal structure, morphology and High temperature 32, 46, 102, 111, 141, 143
crystallite size are adjustable Agglomerate
Hydrothermal Homogeneous component High temperature 143
synthesis Long processing
time
Solegel method Homogeneous component High temperature 18, 108
Agglomerate
Combustion Energy efficiency Long processing 24, 42, 44, 103, 132
synthesis time
Mechanochemical process Room temperature Long processing 17, 80, 144-145
time
Contaminant
Polymeric steric entrapment Homogeneous microstructure Long processing 50
time
Boro/carbothermal reduction High purity High temperature 56-60, 63, 66, 84, 85, 88, 90, 95, 136
Superfine Long processing
time
Molten salt synthesis Nanoflower-like morphology High temperature 68
Long processing
time
Bulk Solid-state Conventional Large size sample High furnace 8, 10, 21, 27e28, 33, 40e41, 47e49, 101, 105e106, 109
synthesis sintering Homogeneous microstructure temperature e110, 146-147
Long processing
time
Spark plasma Fast heating/cooling Small size sample 36, 53, 56, 62, 65e66, 69e70, 72, 75, 77e78, 87, 89, 92,
sintering Short processing time High furnace 93, 98e100, 104, 126, 135
temperature
Nonuniform
microstructure
Flash sintering Room temperature Small size sample 138, 158e161
Ultrashort processing time Nonuniform
microstructure
Containerless solidification Fast heating/cooling Small size sample 52
Ultrashort processing time
Arc melting Fast heating/cooling Small size sample 64
Ultrashort processing time
Thin Pulsed laser deposition Presintered target Long processing 22, 35,162
film time
Magnetron sputtering High purity Long processing 55
time
Varied component

Sarker et al. [73] developed an entropy-forming-ability

0vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi11
(EFA) descriptor as the inverse of the standard deviation of the uPN
u g ðH  H Þ2
energy spectrum above the ground state of the N-system at abso- EFAðNÞ ¼ @t i¼1 Pi i  mix A (9)
N
i¼1 gi  1
lute zero.

Fig. 2. X-ray diffraction patterns demonstrated the reversible entropy-driven phase transformation of high-entropy (Mg, Co, Ni, Cu, Zn)O ceramic. Adapted from a study by Rost
et al. [8] CC-BY-4.0 (https://creativecommons.org/licenses/by/4.0/) (Copyright 2015, the authors, published by Springer Nature.).

4
J. Liu, G. Shao, D. Liu et al.
Fig. 3. Schematic of compositionally complex ceramics (CCCs or C3) or multiprincipal
cation ceramics (MPCCs), and their relationship with high-entropy ceramics (HECs)
and entropy-stabilized ceramics. Adapted from a study by Wright et al. [31] with
permission (Copyright 2020, Elsevier).
where n is the total number of sampled geometrical
configurations and gi represents their degeneracies. Hi is the
enthalpy of the sampled configurations and Hmix is the mixed-
phase enthalpy.
Wen et al. [67] proposed a new method to predict the formation
ability (p) of (MxN1-x)B2 solid solutions using the logistic regression
approach in supervised machine learning,
1 and the charge compensation only comes from the aliovalent cat-
p¼ (10)
1 þ expð  bÞ
h i
0K ;d; VEC; f  ½q ; q ; q ; q ; q T
b ¼ 1; DHmix (11)
0 1 2 3 4
0K , d, and VEC are the normalized values in the range of
where DHmix
0e1 of mixing enthalpy at 0 K and 0 Pa (DHmix 0K ), atomic size dif-
ference (d), VEC, respectively. f is the doping condition, and q1-q4
are the parameters that represent the influence of the aforemen-
tioned four factors on the formation ability. When b > 0, the single-
phase (MxN1-x)B2 solid solutions can be successfully synthesized
and vice versa.
It should be noted that the proposed descriptors for predicting
the formation of single-phase HECs are at the very early stage
similar to HEAs. These descriptors undoubtedly have some
Fig. 4. The strategies of designing mixed-valence complex ceramics. There are three
types high-entropy ceramics with mixed-valence have been explored, including (i)
interstitial oxygen and oxygen vacancy are created to balance the charge in high-en-
tropy non-stoichiometric oxides, (ii) the charge compensation is maintained through
the variable valence states without defect generation, (iii) the charge balance of the B-
site in ABO3 type high-entropy perovskite is compensated by five substituted cations
with different valences in equiatomic amount.
5
Materials Today Advances 8 (2020) 100114
limitations. For example, the proposed descriptor of tolerance fac-
tor (t) was only used for perovskite oxide, and the results did not
agree well with the experiment [33]. However, it provides a facile
route to accelerate the discovery and design process of HECs.
2.4. The frontier of design HECs
To date, HECs with different crystalline structures, composi-
tions, multicationic and multi-anionic structure, and vacancies
have received considerable attention [117e119]. HECs with stable
single-phase structure may not be entropy-stabilized ceramics, but
the phase stability is achieved by the low mixing enthalpy and/or
kinetic effect. Recently, Wright et al. [31,107,137] proposed that
HECs can be expanded to CCCs or multiprincipal cation ceramics
(MPCCs) by including medium-entropy and/or non-equimolar
compositions (Fig. 3). It was found that compositionally complex
fluorite oxides and pyrochlore oxides have reduced thermal con-
ductivity, retained modulus, and hardness. Hence, the CCCs and
MPCCs represent a vast unexplored compositional space besides
HECs [31,107,137].
Moreover, MVCCs are a new type of high-performance HECs
with aliovalent cations and anions (Fig. 4). MVCCs with non-
stoichiometric ratio have been investigated in rock salt oxides
[16e18,130e132], which exhibit excellent catalysis property. Alio-
valent cations and oxygen vacancies have also been introduced into
high-entropy spinel [43], perovskite [36], and fluorite oxides
[26,28,31]. Especially, perovskites with aliovalent cations and oxy-
gen vacancies have shown promising dielectric properties [138].
Recently, Tang et al. [139] proposed a new design strategy using the
method of aliovalent cations combination with stoichiometric ratio,
ions. It was also found that cations with different valence states can
be used to prepare high-entropy oxides with an additional
dimension [139]. Moreover, the cation-valence difference, instead
of cation-size difference, is more correlated to the formation of
ordered structure in stoichiometric high-entropy ABO3 compounds
[139]. Indeed, the method of aliovalent cations combination with
electrical equilibrium provides a good strategy to explore the entire
system and further expand the scope [139].
3. Synthesis of HECs
HEC powder and bulk material have been synthesized through
different routes (refer Table 1). It is desirable to achieve homoge-
neous distribution of the constituent elements at the atomic scale
using low temperature with short reaction time. The typical tech-
niques for preparing HEC powder and bulk material are discussed
in this section, but the wet chemical methods are mainly used for
producing high-entropy oxides now. In particular, the fast solid-
state reaction during reactive flash sintering with applied electric
field will be discussed in detail.
3.1. Wet chemical methods
3.1.1. Flame spray pyrolysis
In the flame spray pyrolysis process [140], the precursor solution
is nebulized within a compressed air nebulizer, and the mist
formed is carried to the flame by oxygen as the carrier gas. Thermal
decomposition/pyrolysis reactions occur in the flame. The resi-
dence time of the particles formed in the flame is very short leading
to rapid heating, as well as quenching. Sarkar et al. [141] synthe-
sized high-entropy (Co, Cu, Mg, Ni, Zn)O and (Co, Mg, Ni, Zn)O using
nitrates as the precursor solution, and liquefied petroleum gas and
oxygen as the fuel and oxidizer for the flame.
J. Liu, G. Shao, D. Liu et al. Materials Today Advances 8 (2020) 100114

3.1.2. Nebulized spray pyrolysis for the hydrothermal treatment. Finally, the product is filtered,
In this technique, the precursor solution is continuously deliv- repeatedly washed with deionized water, and dried at 60  C.
ered into the nebulizer. A mist containing fine droplets of the
precursor solution is formed by an ultrasonic nebulizer, which is
3.1.6. Combustion synthesis
transported by flowing oxygen into the hot-wall reactor to form the
Bhaskar et al. [132] used a mixture of metal nitrates as oxidizers
nanoparticles. The powders are collected using a filter-based col-
and glycine as fuel to synthesize equiatomic (CoCuMgNiZn)O
lector. Using nitrates of the individual metals as precursor, Sarkar
nanocrystalline powder. Mao et al. [24,42,44] prepared (CoCr-
et al. [141] used nebulized spray pyrolysis to synthesize (Co, Mg, Ni,
FeMnNi)3O4 nanopowder using a similar process. Recently, Teng
Zn)O powder at 1,150  C and 1,250  C with a total pressure of
et al. [103] also synthesized (La0.2Nd0.2Sm0.2Gd0.2Yb0.2)2Zr2O7
900 mbar, as well as (Co, Cu, Mg, Ni, Zn)O powder at 1,150  C. Sarkar
nanopowder from mixed metal nitrates and glycine.
et al. [34] also synthesized multicomponent oxides with perovskite
type of structure containing up to 10 different cations in equiatomic
amounts using nebulized spray pyrolysis. Wang et al. [142] used 3.2. Mechanochemical process
equimolar solutions of the respective metal salts to produce Lix(-
NiFeMnCrCo)yOz, Lix(NiFeMnCrMg)yOz, and Lix(NiFeMnZnMg)yOz. Mechanochemical process involves mixing precursor powders
Djenadic et al. [25] prepared water-based solutions using nitrate via high energy ball milling at room temperature to synthesize HEC
salts of Ce, Gd, La, Nd, Pr, and Sm, to synthesize 5- and 6-component powder [17,144,145]. Jin et al. [144] mixed equimolar amounts of
powders of (Ce, La, Pr, Sm, Y)O, (Ce, Gd, La, Pr, Sm, Y)O, and (Gd, La, VCl3, CrCl3, NbCl5, MoCl5, and ZrCl4 in a high-speed vibrating ball
Nd, Pr, Sm, Y)O. mill for 30 min. Then, the resulting gel-like product was pyrolyzed
at 800  C for 3 h under inert N2 atmosphere to form the high-
3.1.3. Coprecipitation entropy metal nitride. Zhang et al. [145] mixed metal chlorides
In this method, a base solution with designed pH level is pre- and aluminum isopropoxide using ball milling for 60 min at a
pared by adding ammonia in deionized water. The precursor so- vibrational frequency of 30 Hz, followed by calcination at 400  C to
lution is added to the ammonia solution in a controlled manner fabricate mesoporous (Cu, Ni, Fe, Co, Mg)OxAl2O3 ceramics. Chen
along with continuous stirring of the mixture at ambient condi- et al. [17] demonstrated that a mixture of five metal oxides (NiO,
tions. After filtering, the precipitate is dried and lightly ground in an MgO, CuO, ZnO, CoO) was completely converted to a single phase
agate mortar and finally calcined at high temperature to obtain the after only 2 h of ball milling with ambient temperature of the
desired crystalline oxide phase. This technique has been widely grinding reactor lower than 70  C. Chicardi et al. [80] successfully
applied by researchers. For example, Sarkar et al. [141] selected
nitrate precursors to maintain the pH level at 10 and calcined them
at 1,000  C for 1 h to produce (Co, Cu, Mg, Ni, Zn)O and (Co, Mg, Ni,
Zn)O powders. Biesuz et al. [143] used zinc (II) sulfate, copper (II)
sulfate, nickel (II) sulfate, cobalt (II) nitrate, and magnesium (II)
nitrate as precursors to synthesize high-entropy (Mg, Co, Ni, Cu, Zn)
O, using potassium carbonate dissolved in deionized water as the
base solution. Chen and Wu [32] dissolved nitrates and potassium
fluoride in deionized water to prepare CeNdCaSrBaF12 nanopowder.
Radon
et al. [46] synthesized amorphous (Zn, Mg, Ni, Fe, Cd)Fe2O4
precursor by simple coprecipitation method. Zhao et al. [111] suc-
cessfully synthesized (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4 and
(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2Zr2O7 [102] using coprecipitation
method.

3.1.4. Sol-gel method

The sol-gel method involves adding ethylenediamine tetraacetic
acid and citric acid to the precursor solution. Then, ammonium
hydroxide solution is added with stirring until the designed pH is
reached and a dark solution is formed. The solution is then stirred
and heated on a hot plate to cause gelation. Finally, the gel is dried,
ground into powder, and calcined at high temperature to form the
HEC. Zhai et al. [18] used the sol-gel technique to synthesize (Fe,
Mg, Co, Ni)Ox, with the precursors of magnesium nitrate hexahy-
drate, iron(III) nitrate nonahydrate, cobalt(II) nitrate hexahydrate,
and nickel(II) nitrate hexahydrate with equimolar cations dissolved
in deionized water. Dong et al. [108] prepared (Yb0.2Y0.2-
Lu0.2Sc0.2Gd0.2)2Si2O7 by the sol-gel method using nitrides and
tetraethoxysilane as the starting materials.

3.1.5. Hydrothermal synthesis

Biesuz et al. [143] used zinc (II) sulfate, copper (II) sulfate, nickel
(II) sulfate, cobalt (II) nitrate, and magnesium (II) nitrate as pre-
cursors to synthesize high-entropy (Mg, Co, Ni, Cu, Zn)O by hy-
Fig. 5. (a) Schematic of flash sintering. (b) The applied field and current density as a
drothermal synthesis. In a typical procedure, the precursor solution function of time during flash sintering mixed Al2O3 and Y2O3 composite powder at
is first mixed with NaOH solution in a Teflon vessel. The Teflon 1,350  C with applied electric field of 55 V/mm and current density of 40 mA/mm2, and
vessel is then sealed and placed in a stainless steel pressure vessel the current surge shows the sintering time can be shortened to a few seconds.

6
J. Liu, G. Shao, D. Liu et al.
Fig. 6. (a) Plots of applied field, current density, and power dissipation as a function of
time for flash sintering mixed high-entropy (Mg, Ni, Co, Cu, Zn)O powder at room
temperature with the electric field of 250 V/cm and current density limit of 80 mA/
mm2.(b) Typical XRD patterns of presintered and flash sintered (Mg, Ni, Co, Cu, Zn)O
samples. (a) and (b) adapted from a study by Liu et al. [159] with permission (Copy-
right 2020, Elsevier).
synthesized high-entropy (TiZrHfVNb)C5 powder by a mechano-
chemical synthesis process from the elemental mixture.
3.3. Solid-state synthesis
3.3.1. Conventional sintering
Generally, the solid-state synthesis method includes two steps.
First, the precursor powders are thoroughly mixed using ball
milling. Second, the mixed powder is heat treated at high tem-
perature to obtain HEC powder or bulk material. Rost et al. [8] used
the solid-state synthesis route to prepare the first entropy-
stabilized (Mg, Ni, Co, Cu, Zn)O ceramic. Be
rardan et al.
[10,21,146] synthesized (Mg, Co, Ni, Cu, Zn)1-xLixO, (Mg, Co, Ni, Cu,
Zn)1-xNaxO, (Mg, Co, Ni, Cu, Zn)1-2xLixGaxO, (Mg, Co, Ni, Cu,
Zn)0.95K0.05O, and so on from binary oxides and carbonates. Bal-
cerzak et al. [147] used oxide powders with equimolar proportions
as precursor and mixed them in a shaker-type ball mill for 100 h in
air followed by thermal treatment to obtain high-entropy oxide.
Chen et al. [27] mixed the five-component CeO2-ZrO2-HfO2-SnO2-
TiO2 system and obtained single-phase (Ce0.2Zr0.2Hf0.2Sn0.2Ti0.2)O2
after sintering at 1,500  C for 6 h followed by cooling down in the
7
Materials Today Advances 8 (2020) 100114
furnace. Gild et al. [28] used HfO2, ZrO2, CeO2, TiO2, Y2O3, Yb2O3,
La2O3, Gd2O3, CaO, and MgO as the starting materials to synthesize
high-entropy fluorite oxides with 12 different compositions. Vinnik
et al. [47e49] sintered oxides and carbonates at high temperature
to prepare a series of high-entropy single-phase products with
BaFe12O19 (magnetoplumbite) structure containing doping ele-
ments at high concentration level. Jiang et al. [33] partially
substituted Ti of SrTiO3, BaTiO3 and (Sr0.5Ba0.5)TiO3 with equal
molar fractions (1/4 or 1/5) of several elements selected from
among Zr, Sn, Hf, Mn, Nb, Ce, Ge, and Y to synthesize high-entropy
perovskite oxides by high-energy ball milling followed by sintering.
In another study, (Na0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3 powder was pre-
pared via solid-state method by Pu et al. [40] using high-purity
Na2CO3, Bi2O3, BaCO3, SrCO3, CaCO3, and TiO2 as starting pow-
ders. Da˛ browa et al. [41] synthesized high-entropy (Co, Cr, Fe, Mn,
Ni)3O4 oxide with spinel structure from MgO, ZnO, CuO, NiO, MnO,
Fe2O3, Co3O4, and Cr2O3 via milling and sintering. Solid-state re-
action method has also been used to prepare high-entropy silicates
[109,110] and pyrochlore oxides [101,105,106].
3.3.2. Spark plasma sintering
Spark plasma sintering (SPS) has been used in solid-state syn-
thesis method to replace conventional sintering due to its shorter
sintering time, higher heating rate, and enhanced densification
[135]. Hong et al. [135] used SPS to synthesize high-entropy (Mg,
Co, Ni, Cu, Zn)O. Biesuz et al. [36] synthesized high-entropy
perovskite Sr((Zr0.94Y0.06)0.2Sn0.2Ti0.2Hf0.2Mn0.2)O3x from the ox-
ide powder mixture. Li et al. [126] synthesized single-phase tita-
nium-zirconium oxycarbonitride ceramics Ti1/2Zr1/2 (C1/3N1/3O1/3)
by SPS of the corresponding Ti and Zr oxides, carbides, and nitrides.
Gild et al. [53,62] prepared seven equimolar, five-component, metal
diborides via high-energy ball milling and SPS. Shen et al. [56]
consolidated the high-entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder
via SPS to produce bulk high-entropy diboride ceramic. Tallarita
et al. [61,65] synthesized (Hf0.2Mo0.2Zr0.2Nb0.2Ti0.2)B2 from
elemental reactants using SPS. In addition, SPS has also been widely
used to produce different high-entropy carbides
[69,70,72,75,77,78,87,89,92,93], silicides [98e100], and zirconates
[104].
3.3.3. Flash sintering
Recently, it has been demonstrated that the use of critical
electric field can accelerate solid-state reactions and induce phase
transition during flash sintering [148e150]. As a result, the sinter-
ing time can be shortened to a few seconds (Fig. 5). It is hypothe-
sized that internal reactions [151,152], avalanche of Frenkel pairs
[153], and fast joule heating [154,155] likely contribute to the ul-
trafast mass transportation during flash sintering. On the other
hand, flash sintering leads to ‘softening of lattice’ [156e158], which
can be beneficial for the atomic mixing and phase transformation of
HECs. Hence, this provides a new approach to synthesize HECs. Liu
et al. [159] successfully synthesized five-component entropy-sta-
bilized oxide ceramic (Mg, Ni, Co, Cu, Zn)O by reactive flash sin-
tering at room temperature. It was found that the mixed oxides
were completely transformed to a single rock salt phase in just a
few seconds (Fig. 6), and the internal reactions and high concen-
tration of oxygen vacancies under the applied electric field were
believed to be responsible for the significantly accelerated phase
transformation [159]. Concurrently, Yoon et al. [160] and Kumar
et al. [161] also presented similar results, but the furnace temper-
ature was much higher during their flash sintering process. Reac-
tive flash sintering has also been successfully used to produce high-
entropy Sr(Ti0.2Y0.2Zr0.2Sn0.2Hf0.2)O3-x by Wang et al. [158] at low
temperature within short time. It was found that the rapid for-
mation of single-phase oxide enhanced the diffusion rate and also
J. Liu, G. Shao, D. Liu et al.
softened the lattice under critical electric field [158]. Recently, Liu
et al. [138] used a stepwise current-ramping flash sintering process
to synthesize and densify (Bi0.2Na0.2K0.2Ba0.2Ca0.2)TiO3 ceramic.
Excessive Naþ and Kþ ions were obtained in the single-phase high-
entropy perovskite ceramics due to the low sintering temperature
and rapid processing with applied electric field [138]. It was found
that charge compensation and valence state alteration occurred
during flash sintering, thus providing a viable strategy to tune the
properties of HECs [138].
3.4. Other methods
The methods for preparing HECs are many and varied. In addi-
tion to the aforementioned preparation methods for high-entropy
oxide ceramics, researchers have attempted many other methods to
synthesize HECs. For example, Sharma et al. [35] used pulsed laser
deposition to grow perovskite Ba(Zr0.2Sn0.2Ti0.2Hf0.2Nb0.2)O3
epitaxially on SrTiO3 and MgO substrates. Pulsed laser deposition
was also used to synthesize (MgCoxNiCuZn)O film [22] and
MgxNixCoxCuxZnxScxO film [162]. Mayrhofer et al. [55] used non-
reactive magnetron sputtering to prepare high-entropy (Zr, V, Ti,
Ta, Hf)B2 coating.
In a different approach, Tseng et al. [50] synthesized single-
phase high-entropy, lanthanide oxide using a polymeric steric
entrapment method. Zhang et al. [52] prepared amorphous high-
entropy oxide ceramic 10La2O3-20TiO2-10Nb2O5-20WO3-
20ZrO2 by containerless solidification. Borothermal/carbothermal
reduction method has been used by several researchers to syn-
thesize high-purity high-entropy metal diboride powders
[56e60,63,66]. Moreover, carbothermal reduction of oxides has
been widely used to synthesize high-entropy carbide powders
[84,85,88,90,95,136]. Failla et al. [64] used arc melting to produce
dense high-entropy metal diborides starting from HfB2, ZrB2, TiB2,
TaB2, and CrB2 powders. Liu et al. [68] successfully synthesized
(Ta0.2Nb0.2Ti0.2W0.2Mo0.2)B2 high-entropy diboride nanoflowers by
a facile molten salt synthesis method. Li et al. [79] reported a simple
liquid precursor method for the synthesis of single-phase high-
entropy carbide nanopowders using transition metal halides (TiCl4,
ZrCl4, HfCl4, NbCl5, TaCl5) and furfuryl alcohol as metal sources and
carbon source. Undoubtedly, more and more synthesis methods
will be developed with the rapid expansion of HECs.
4. Summary and outlook
Since 2015, HECs have become increasing popular in the
research field due to the unique properties of high-entropy oxides,
high-entropy ultrahigh temperature ceramics/coatings, and high-
entropy thermoelectric materials, such as dielectric, magnetic,
catalytic, energy storage, thermal, and mechanical properties. The
idea of HECs emerged from HEAs. Hence, the fundamental under-
standing of HECs was born out of HEAs, but the diversity and
specificity of ceramics have not been sufficiently explored until
now. For example, cation and/or anion sublattices provide much
higher configuration entropy than HEA with simple crystalline
structure, which increases the compositional space of HECs
significantly. Hence, the single phase can be easily achieved in CCCs
with medium-entropy and/or non-equimolar compositions.
Although the fundamental understanding of the formation crite-
rion is still at the very early stage, which limits the discovery and
design process of HECs. Wright et al. [31,107,137] proposed to
expand HECs to CCCs, including medium-entropy and non-equi-
molar compositions, which will stimulate the research on diverse
ceramics from the perspective of entropy.
Charge balance alters the valence state and/or defects in HECs,
which provides the possibility to tune the defects, order, and
8
Materials Today Advances 8 (2020) 100114
disorder structure. On the other hand, the method of aliovalent
cations combination [139] can shrink the compositional space to
pursue HECs with ordered structure. Hence, the high-entropy ox-
ides, ultrahigh temperature HECs/coatings, and high-entropy
thermoelectric materials should be designed from the perspective
of aliovalent cations and/or defects besides the atomic radius. It will
open a new window for pursing the HECs with excellent energy
storage, catalytic activity, conduction, dielectric, thermoelectric,
and magnetic properties, as well as mechanical properties.
Wet chemical methods have been widely used to synthesize
HEC powder, which are similar to the previous processes except for
the complex precursor materials. Solid-state synthesis is a common
method based on mass diffusion at high temperature to gain bulk
HECs. However, the slow diffusion process requires long heating
times to achieve uniform elemental distribution and high density.
SPS provides fast heating rate, as well as accelerates the dissolution
and densification processes. Thus, SPS has been widely used to
synthesize ultrahigh temperature HECs.
Recently, it was demonstrated that reactive flash sintering
reduced the sintering time to several seconds [158,159], which is
order of magnitude faster than traditional sintering and SPS. The
applied electric field softens the lattice and induces higher lattice
tolerance of HECs than conventional sintering method. The charge
compensation mechanism in the flash sintered HECs provides a
viable strategy to tune the dielectric properties. It is anticipated
that the proposed strategy would be applicable for developing
other HECs with excellent functional and mechanical properties.
In addition, compacting the synthesized HEC powder using
different sintering methods should be a future direction. The grain
boundary engineering is possible to improve the mechanical,
chemical, electrical, and magnetic properties of bulk HECs.
Author contributions
Jinling Liu: Conceptualization, Methodology, Writing - Original
Draft, Writing - Review & Editing Gang Shao: Data curation Dia-
nguang Liu: Data curation Kepi Chen: Writing - Review & Editing
Kewei Wang: Data curation Baisheng Ma: Data curation Ke Ren:
Data curation Yiguang Wang: Conceptualization, Methodology,
Supervision
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
This work was financially supported by the National Natural
Science Foundation of China [Grant Nos. 51672227, 51732009 and
51802271] and Fundamental Research Funds for the Central Uni-
versities (Grant No. 2682020ZT38).
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