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Recent advances in interface engineering of

thermoelectric nanomaterials
Cite this: Mater. Chem. Front.,
2023, 7, 4707
Xiaoqing Lu,†a Guilong Pan,†a Zhan Shi, b
Biao Xu *a and Yue Lou *a

Received 19th April 2023,
Accepted 15th June 2023
DOI: 10.1039/d3qm00419h
rsc.li/frontiers-materials
Thermoelectric (TE) materials are auspicious candidates for direct thermal–electrical energy conversion
applications. Interface engineering is one of the key parameters to determine the physicochemical prop-
erties of nanocomposites, in which interfacial manipulation can reduce k by nano/micro-scale grain
boundary construction and increase the power factor by electronic structure modifications, ultimately
leading to an increase in ZT. With the advancement of nanotechnology, the design and synthesis of
nanoparticles can be extended to sub-nanometer and even single-atom scales, which provides an
opportunity for developing novel materials with extraordinary thermoelectric performances. In this
article, we have chosen a completely new field – interface and provide a comprehensive review of the
interfacial manipulation of hybrid materials, which are discussed in four parts chosen according to their
dimension forms, including atoms, nanoclusters, ligand molecules, and particles. We also analyze the
interaction of nanoparticle surfaces and identify the possibilities and obstacles for improving the perfor-
mance of TE materials.

1. Introduction
Since the 21st century, over-exploitation and consumption
of non-renewable energy sources have aggravated the energy
crisis. Only about 30% of the thermal energy can be used, and
the rest is emitted into the atmosphere as ineffective waste
heat, which further leads to a series of environmental problems
such as global warming. Therefore, researching new materials
related to the development and utilization of renewable energy
is imperative.11 Among those new energy materials, thermo-
electric (TE) devices not only can directly convert thermal
energy to electrical energy, but also have the advantages of no
moving parts and no pollution.12 Therefore, TE materials have
been considered as promising materials for solving environ-
mental problems and energy crises.
The properties of TE materials are measured using the
dimensionless thermoelectric figure of merit ZT = S2sT/k, where
S is the Seebeck coefficient, s is the electrical conductivity, T is the
absolute operating temperature, and k is the total thermal con-
ductivity. Usually, the total thermal conductivity k consists of two
components, k = ke + kl, where ke is the carrier thermal conduc-
tivity and kl is the lattice thermal conductivity. In order to obtain a
a
Department of Chemistry and Chemical Engineering, Nanjing University of Science
and Technology, Nanjing, Jiangsu 210094, P. R. China.
E-mail: xubiao@njust.edu.cn, louyue@njust.edu.cn
b
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,
College of Chemistry, Jilin University, Changchun 130012, P. R. China
† These two authors contributed equally.
high ZT, TE materials must have high S, high s and as low as
possible k values.13–15 However, optimizing the TE performance
is a relatively complex task due to the intercorrelation of the S,
s, and k parameters using eqn (1)–(4):16,17
8p2 kB2   p 3
2
S¼ m T (1)
3eh2 3n
s = nem (2)
ke = LsT (3)
1
kl ¼ CV vl (4)
3
where n, e, m, h, kB, m*, L, CV, n, and l stand for the carrier
concentration, elementary charge, mobility, Planck constant,
Boltzmann constant, carrier effective mass near the Fermi level,
temperature-dependent Lorenz number, specific heat at con-
stant volume, phonon propagation rate, and mean free path,
respectively. In general, S, s and ke belong to the electronic
relations, which are closely related to n. The increase of n will
lead to a smaller S value and an increase in the ke value, and the
three parameters are strongly coupled with each other.18–20 The
kl depends on the phonon transport and can be individually
tuned by introducing various phonon scattering mechanisms.
In summary, coordinated regulation of the electrons and
phonons is difficult to achieve, making the optimization of
TE material properties extremely challenging.
Based on previous theoretical analysis, directions for further
optimization of TE material properties are pointed out. On the

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Fig. 1 (a) s, S, PF, k, and n relationships of materials. (b) Schematic of crystal defect manipulations. (c) Timeline for the state-of-the-art thermoelectric
materials (bulks), including Bi2xSbxTe3(BST), BiCuSeO, clathrates, Cu2xSe, GeTe, half-Heuslers, Sn1xSe, PbTe, skutterudites, SnTe, and Zintls. Copyright
2020, American Chemical Society.
electrical part, the most typical strategies are the realization of
multiple energy band simplifications or the introduction of
additional electronic resonance energy levels through solid
solutions. Based on energy band engineering, large S can be
obtained by optimizing the effective density of states of the
material near the Fermi surface while avoiding degradation
caused by additional scattering of carriers as much as
possible.21,22 In addition, high s can be achieved by directly
adjusting the n through appropriate doping and defects. When
the carrier reaches a certain concentration, the PF will reach a
maximum (Fig. 1a). On the thermal part, introducing a multi-
scale structure to lower the mean free range of phonons to
reduce kl is worthy of acceptance, as shown in Fig. 1b.23–25
Meanwhile, the successful preparation of superlattice thin film
TE materials experimentally confirms the effectiveness of nano-
scale effects in modulating the TE transport properties. A low
dimension leads to a significant increase in the density of
states near the Fermi surface of the superlattice material, which
leads to an increase in S. In addition, a low dimension can
reduce k by increasing interfacial phonon scattering through
quantum size effects and quantum wells. Thus, a low dimen-
sion can simultaneously optimize the thermal and electrical
properties to achieve a significant increase in ZT. Fig. 1c
presents the ZT values of these materials measured in the last
decade.26 Nowadays, most of the articles improve the TE
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properties of materials by inducing doping or reducing the
dimensionality. Zhou et al.27 found that benefiting from Na-
doping, the ZT value of the polycrystalline SnSe has reached 3.1
at 783 K. Liu et al.28 reported that PEDOT: PSS films show ultra-
low k due to its low dimension. The induced doping strategy
was used to enhance both S and s, which in turn enhanced the
electrical properties.
In this work, we wrote from a different perspective: inter-
facial manipulation to minimize the overlap with many existing
review articles in the TE field. This perspective is dedicated to
discussing various strategies for the preparation of nanomater-
ials with surface treatments. Firstly, from the synthesis strategy,
we focus on introducing the effect of different solution synthesis
strategies on the nanoparticle size, morphological and surface
ligands, and their effect at the interface. Next, four components
are selected to discuss the interfacial modifications according to
the multidimensional interface engineering design, including
single atoms, clusters, ligand molecules, and the second phase,
as shown in Fig. 2.
2. Solution synthesis method
From the perspective of material design and synthesis, achieving
precise regulation of the interface structures is a new path to

Materials Chemistry Frontiers
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Fig. 2 Four kinds of thermoelectric composites: thermoelectric substrates/single-atoms, thermoelectric substrates/clusters, thermoelectric substrates/
ligands, and thermoelectric substrates/second-phase.
improve the performance of thermoelectric materials.29 Unlike
the conventional solid-phase synthesis method, the solution
synthesis method not only has the benefits of low cost and
simple operation, but also allows unprecedented modulation of
their surface, crystal structure, size, and shape.30,31 Common
solution synthesis methods include ‘‘top-down’’ liquid strip-
ping and ‘‘bottom-up’’ hydrothermal/solvent thermal and wet
chemical methods.
2.1 ‘‘Top-down’’ liquid stripping method
‘‘Top-down’’ solution synthesis refers to the preparation of
larger-sized substances into the nanostructures that we need
through various techniques.32 Ambrosi et al.33 proposed a
simple and fast electrochemical method to exfoliate natural
Bi2Se3 and Bi2Te3 crystals into monolayers/several thin layers in
aqueous media. The oxidation state of both Bi and Te was
found to be higher than that of the natural Bi2Te3 bulk crystals
and showed higher binding energy properties according to the
XPS characterization technique.
2.2 ‘‘Bottom-up’’ solution synthesis method
The ‘‘bottom-up’’ solution synthesis method refers to the self-
assembly of smaller structural units (such as atoms, molecules,
nanoparticles, etc.) into relatively large structural systems
through weak interactions.34 The bottom-up liquid sintering
approach can synthesize bulk composites with a hierarchical
structure, which effectively enhances the phonon scattering at
the interface, leading to a significant decrease in the kl value of
the material. It also leads to a boost in PF, which is attributed to
the increase in n.35,36 Nowadays, there is increasing research on
TE materials with solution-processed nanostructures. In this
review, we look specifically at interface modification based on
the ‘‘bottom-up’’ solution approach.
2.2.1 Hydrothermal and solvothermal methods. Hydro-
thermal and solvothermal methods are effective methods for
inorganic synthesis and materials processing. Aqueous or
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organic solvents are used as the reaction system in a specific
reaction vessel (reactor) to dissolve and recrystallize insoluble
substances by heating and pressurizing. The reaction system
provides a relatively high temperature and pressure environ-
ment.37 Li et al. performed a four-point probe technique on
CoSb3 skutterudite TE materials synthesized by hydrothermal
and solvothermal methods and found that the hydrothermally
prepared samples had a significant advantage, with a 14%
increase in S, a 5% decrease in k, and a 33% increase in ZT
at 725 K. Meanwhile, the hydrothermal method is safer, more
cost-effective and environmentally friendly.38 In addition,
according to the microstructural characterization, it was found
that the samples prepared using a hydrothermal method had
well-developed and uniformly distributed grains, and it was
easier to obtain suitable crystalline shapes.39 Zhang et al.
synthesized PbS using a hydrothermal method combined with
high-pressure sintering, and the SEM results showed that the
PbS samples prepared using the hydrothermal method had
sub-cubic shapes, while good crystallization and grains were
retained after high-pressure sintering.40
2.2.2 Colloidal chemical method. Colloid chemistry is a
method for studying the interfacial phenomena of dispersed
systems and their physicochemical and mechanical properties.
Colloid chemistry is mainly used to study the interfacial
phenomena, the nature of the interfacial layer and the condi-
tions of existence of the dispersed system and the factors
affecting the stability of the system. In recent years, colloidal
synthesis methods have shown significant practical value in the
direction of synthesizing nano thermoelectric materials.41 In a
typical colloidal synthesis, heating techniques and thermal
injection methods are the two common methods. In the
presence of ligands and organic solvents, the anion source is
rapidly injected into the hot metal precursor solution, and then
nucleation begins.42
2.2.3 Wet chemical method. Wet chemistry is a generic
method that involves the liquid phase and the preparation of

Review
materials by chemical reaction. The wet chemical method
in the synthesis process is first to select one or several soluble
metals or oxides needed to prepare a solution, and then through
precipitation, evaporation, sublimation and other operations to
obtain materials. Wet-chemical synthesis in aqueous or organic
medium is one of the most dominant approaches among
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the bottom-up ones to produce nanoparticles with tailored
characteristics.43,44
3. Interface engineering
Modulating the thermoelectric properties of materials through
interface engineering is an effective strategy.45 On the one
hand, it can produce an energy filtering effect by regulating
the dispersion of low-energy carriers without disturbing the
potential barrier of high-energy carriers. Scattering of more low-
energy carriers rather than high-energy carriers occurred and S
increases.46 On the other hand, the introduced second phase
and phase boundary can strongly scatter phonons. However,
the presence of an interface also usually increases the resistivity
due to the insulation overlay, resulting in low s.47 Therefore, an
effective balance between the thermal and electrical properties
of the interface is essential.48 A well-designed interface should
be able to scatter phonons and low-energy carriers strongly
without sacrificing s.
3.1 Single atoms and clusters
3.1.1 Single-atom modulation. With continuous advance-
ment of nanotechnology, chemists have control over synthesis
up to the sub-nanometer and even single-atom scales.49 At this
new scale, the ratio of surface energy to total energy increases
dramatically due to a sharp increase in the proportion of
surface atoms. This alters thermodynamic relationships within
conventional crystals, resulting in entirely new atomic arrange-
ments and new electron and phonon structures. Therefore,
from the unique perspectives of maximized atom utilization
efficiency,50 an unique electronic structure,51 guest–host inter-
actions52 and a tunable coordination environment,53 single-
atom materials have a wide range of applications in thermo-
electric fields.
Our group54 has synthesized a single-atom TE material
Bi2S3-0.5 wt% Pt1, using the solvent thermal synthesis method
combined with the syringe pump method, demonstrating
the possible future development path of single-atom-based TE
materials for the first time. Relying on the high-angle annular
dark field scanning tunneling electron microscopy (HAADF-
STEM) characterization technique and energy dispersive spectro-
scopy (EDS) elemental mapping (Fig. 3a), it was proved that Pt
elements uniformly dispersed on Bi2S3 nanowires and there was
no aggregation of Pt atoms in Bi2S3-0.5 wt% Pt1 samples.
Extended-edge X-ray absorption fine structure spectroscopy
(EXAFS) shows the presence of Pt–O and Pt–S bonds in the
sample (Fig. 3b), further confirming the successful coordina-
tion of individual Pt atoms to the Bi2S3 nanowires. The unique
coordination relationship between the Pt species and Bi2S3
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regulates n and m effectively, which leads to a significant
increase in s with an increase in the Pt content. Multiple
scattering mechanisms act in concert in the Bi2S3–Pt1 sample,
especially doping and introduction of the dislocation density,
which suppress k to 0.37 W m1 K1 at 823 K significantly.
Ultimately, the maximum ZT value for Bi2S3-0.5 wt% Pt1
reaches B0.75 at 823 K, with an average ZT value of 0.39 from
323 to 823 K. This success makes the use of single atoms in
other TE material systems possible.
3.1.2 Cluster modulation. In addition to single atoms,
clusters also play an important role in regulating the thermo-
electric properties.55 The size of ultra-fine clusters is slightly
larger than atoms, and the presence of clusters effectively
suppresses phonon transport and ionization energy on the
interface. Liu et al. found that the interfacial thermal resistance
can be effectively reduced by increasing the interfacial density
of clusters in nanocomposites.56 It was found that a high
conductivity layer was formed at the interface, leading to a
simultaneous increase in s and S. It achieved a PF of up to
224 mW m1 K2, and the k reached 0.39 W m1 K1 at 410 K
due to the increase in phonon scattering. Moure et al.57 com-
bined the semiconductor CoSb3 and nano-oxide junction clus-
ters to form nanocomposites. The functional interface formed
effectively decouples k and s, in which the functional interface
as a phonon scattering center can greatly reduce k, and a high
s is achieved by selective doping. Ultimately, the composite
reaches a ZT value of 1.
3.2 Ligand molecular modification
Nanocrystals (NCs) are important components of TE materials
due to their controlled shape and size.58 Ligands are respon-
sible for the properties of the inorganic NC core because they
play a key role in regulating NC nucleation and growth, which
influence the material dispersion properties and colloidal
stability through the hydrophilic–lipophilic balance.59,60
In the process of colloidal synthesis, organic surfactants
such as oleylamine (OAm), oleic acid (OAc), phosphonic acid
(PA), etc. are commonly used.61 Conventional common treat-
ments such as ligand exchange have been widely investigated
by employing small-volume inorganic ligands or short-chain
organic ligands to replace natural long-chain organic ligands.62
Recently, a ligand retention strategy has been proposed by our
group.63,64 By compressing nanocrystals or changing the sam-
ple element ratios to form unconventional phases without
eliminating long organic ligands, unprecedented enhancement
of the TE properties of the materials is obtained. In this section,
we will review the role of ligands in the morphology, stability
and function of nanoparticles (NPs), thereby analysing the NC
surface, the interaction of ligands with different chemical
groups and their effect on TE properties.
3.2.1 Exchange of ligands. There are several limitations to
be overcome to take full advantage of NCs for the production
of functional nanomaterials. First, the electrically insulating
barrier on the surface of these crystals hinders the charge
transfer between the nanocarbons and the medium.59 Next,
due to the high boiling point of these long-chain surfactant-like
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Fig. 3 (a) The HAADF-STEM image of Bi2S3-0.5 wt% Pt1 and its crystal structure, SAED, and EDS elemental mapping analysis. In the relative elemental
analysis, the green, yellow, and red colors represent Bi, S, and Pt elements, respectively. (b) Corresponding FT-EXAFS curves and their fitting
lines. Copyright 2022, American Chemical Society. (c) EDA-mediated ligand exchange on the oleophilic QD ‘‘Surface’’. Copyright 2013, American
Chemical Society. Schematized view of the displacement of TOP molecules from the surface of Ag2Te nanocrystals. Copyright 2013, Royal Society of
Chemistry.

molecules, residues are left when they are annealed under an
inert atmosphere. Residues may affect the series resistance,
and thus affect the charge transport efficiency potentially.58
Therefore, the application of NC on most material devices
(optoelectronic, thermoelectric, catalytic) is severely limited.
Many research teams have taken constant concern about
exchanging ligands to make them functional materials with
excellent performance.59
3.2.1.1 Inorganic ligand exchange. Inorganic ligands are pro-
mising capping ligands because of their small size, stability,
and high m,65 and the modification of NC surfaces can improve
the transport properties effectively. The most common
inorganic small molecules used for surface functionalization
are thionates, metal thionates, halides, and metalates.66 Ibanez
et al. extensively investigated the exchange of thionates and
metal thionates.67–69 The common exchange is to use colloidal
NCs as an initial building block for the substitutional doping
of ions and exchange the ligands of thiolate compounds with
natural organic surface molecules, subsequently thermal soli-
difying into dense solids. For example, PbS NCs are used as
starting building blocks for ligand exchange reactions with
natural organic surface molecules via alkali metal sulfide
compounds (K2S, K2Te, Na2S).70 Then heat-solidification into
dense modules and substitution doping of ions is achieved
during annealing. The electrical property tests revealed that
the K2Te–PbS composites exhibited a strong p-type behavior
and the samples were present with a high s value, a Hall
concentration of about 3  1019 cm3 and an S value of about
222 mV K1. In addition, Ibanez et al. proposed a bottom-up
approach for the preparation of pb–Ag–K–Se–Te composites.71
The tips of the original PbS nanorods that were made of Ag2S
and K+ was introduced by replacing the K2Te for the original
organic to form a five-component nanocomposite. Due to the

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mixed doping of the crystalline phase particles, k was effectively
suppressed and efficient p-type transport was obtained. Ultimately,
the sample has a ZT value of about 1 at 620 K.
It is worth mentioning that using appropriate surface
ligands can not only balance the ratio between surface cations
and anions in polar compounds, but also can modulate n.
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It can be seen that the sulfur group of small molecules has a
significant effect on the material TE property enhancement.
The use of halide passivation and surface metal cations has
been proven to be effective in controlling the surface charge
of NP, while preventing the formation of deep electronic traps
by avoiding oxygen absorption. In the thermoelectric field, one
method of removal uses an inorganic strong acid (HCl).72 This
procedure uses a ligand exchange step to remove carboxylic
acids from the NP surface while adding a controlled concen-
tration of halide ions. After solidification of the NP into dense
pellets, the halide ions diffuse into the crystal structure, doping
the anionic sublattice and achieving n-type electric doping.
Last but not least, the use of some sulfates may change the
chemical composition of NC-based materials. The use of some
halide ions for ligand exchange may change the properties of
the material. Here, Doris et al.73 proposed a scalable and
general procedure to use Ag2Te as the model material to replace
organic ligands from NC surfaces with metal salt solutions
without introducing external impurities. When the organic
ligand was replaced by AgNO3, the TE figure of merit of Ag2Te
was increased by a factor of 6 (Fig. 3d). In addition, the oxygen
anions (PO43, MnO42) exhibited higher stability and enriched
the inorganic ligand family.74
3.2.1.2 Organic ligand exchange. Short-chain organic ligands
are slightly larger in size than inorganic ligands and exhibit
different electron affinity and binding behavior on the NC
surface. Common shorter small molecule organic ligands
include ethylenediamine (EDA), ethylenedithiol (DDT), hydra-
zine (NH4), thiol (TH), etc.75 Sun et al. systematically investi-
gated the effect of three organic small molecules, EDA, DDT,
and NH4 on the TE properties of Ag2Te nanocrystals prepared
by the dipping coating method. Through the analysis of experi-
mental results, it was found that the incorporation of small
molecules into specific nanocrystalline films resulted in higher
PF and lower s, thus improving the properties at room tem-
perature. Compared to long-chain organic ligands, they will
maximize the reduction of charge transport barriers and main-
tain high s.76
Dai et al. demonstrated a simple and versatile method using
exchange reactions of EDA with the original organic ligand to
transfer the oleophilic quantum dots (QDS) to the aqueous
phase. The transfer efficiency was found to be up to 100%
based on the critical role of the addition of EDA ligands.
In addition, the surface reaction of QDS capped with EDA
showed quite high reactivity (Fig. 3c). It was found that amines
and NH4 did not exhibit strong exchangeability. Residual
carbon could still be observed adhering to the particle surface,
affecting the chemical stability.77 Matthew et al.78 used TH-
encapsulated bismuth telluride single crystal NPs and carefully
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removed the capping agent by high-temperature annealing.
The annealing improved the TE properties as confirmed by
Hall effect tests. The k was more than two times lower than that
of the optimized commercial bismuth telluride alloy. By com-
paring the NPs prepared with bismuth telluride capped with
thiol and without any capping agent, Purkayastha et al.79 found
that capping them with TH molecules not only reduced agglo-
meration but also inhibited the formation of surface oxides.
Then, the s and S values of the Bi2Te3 NP films were measured.
It was found that the NP is an n-type semiconductor and
exhibited a very high S value of about 107 mV K1.
In conclusion, it was experimentally demonstrated that the
incorporation of organic small molecule ligands in NCs can
achieve a higher PF and a lower k value.
3.2.2 Ligand retention. Compared to the conventional
strategy of removing the limitations in material performance
applications by ligand stripping, our group innovatively
demonstrated a new synthetic route of surface ligand retention,
as is shown in Fig. 4. Zhang et al.63 retained OAm and DDT
coated on the surface of nanocrystals in the preparation of
high-entropy nanostructured solids (Fig. 4a). It was found that
OAm acts as a colloidal NC surfactant. It reduces the free energy
on the NC surface and passivates the crystalline surface of
wurtzite nanocrystals, inhibits the grain size, and thus stabi-
lizes the metastable phase. Finally, the TE properties of these
dense materials compacted by NC were characterized and it was
found that the materials exhibited a high PF (0.44 mW m1 K2)
and an ultra-low k value (0.25 W m1 K1). The nanostructured
sample Cu1.87Ag0.13(In0.06Sn0.94)Se2S has a ZT value of 1.52 at
873 K, which is 204% higher than that of intrinsic Cu2SnSe3.
This work provides directions for inducing small-sized stable
metastable phases by ligand retention. In another scientific
work (Fig. 4b), Li et al. obtained the phase connection between
the conventional monoclinic (m) phase and the unconventional
metastable (t) phase as a result of retaining the ligand DDT
instead of the conventional method of stripping the ligand.64
T-phase doping significantly increases the n value and electrical
transport, leading to an enhancement of the PF. At the same
time, it increases phonon scattering and leads to a substantial
decrease in k. Ultimately, the ZT value in the (m-Cu2S)0.31-
(t-Cu1.96S)0.69 sample reaches 2.11 at a temperature of 923 K.
This work provides a paradigm for the enhancement of TE
properties by modulating the phase-junction through surface
ligand retention. Two research studies confirm that the TE
properties of the materials were substantially improved, provid-
ing a model for enhancing the TE properties through surface
ligand retention modulation.
3.3 Second-phase precipitation
In addition to the several methods of interfacial modification
summarized above, the TE performance of materials can also
be improved by introducing new materials doped to form a
second phase. The introduction of the second phase is an
artificial modification that forms a multiphase composite
material by entering the material’s matrix and improving the
TE properties in different ways. Numerous studies have shown
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Fig. 4 (a) Synthetic methods of the metastable wurtzite structure Cu2yAgy(InxSn1x)Se2S nanocrystals and metastable cubic Cu2yAgy(InxSn1x)Se2S
nanostructured solids. Copyright 2022, the Royal Society of Chemistry. (b) Schematic diagram of the surface ligand (decanethiol) directed strategy for the
preparation of Cu2S nanomaterials with phase junction interfaces between monoclinic and tetragonal phases. Copyright 2022, Wiley.

that the introduction of a second-phase dispersion mainly
improves the TE performance by optimizing the thermoelectric
transport mechanism of carriers. Firstly, the difference in size
between the second phase dispersion and the TE matrix is
bound to lead to the formation of a high-density interface,
which will allow for more efficient phonon scattering. During
thermal transport, the lattice thermal conductivity shows a
significant reduction independent of carrier transport due to
the large size of the interface formed between the second phase
and the TE matrix. The thermoelectric properties of the mate-
rial are enhanced in the low and medium temperature sections.
During the electrical transport, a potential hydrazine or barrier
may form due to the energy difference between the second
phase and the TE matrix, which allows the passage of high-
energy carriers while filtering low-energy carriers. This
energy filtering effect (which can also be described as selective
filtering or scattering) can substantially increase S without
sacrificing s.80–86
3.3.1 Metal. Introducing metal atoms as the second phase
directly allows optimizing the electronic structure and arrange-
ment of atoms, resulting in lower kl and enhanced PF.87
Tian et al.88 used a chemical plating method combined with
the spark plasma sintering (SPS) process to apply the interfacial
modification technique to Ag-plated SnTe blocks. After sintering,
the Ag second phase was doped in SnTe, which suppressed the
formation of Sn vacancies and was beneficial for the electrical
transport properties. A high-density Ag/SnTe interface was further
formed between the Ag second-phase dispersion and the SnTe
matrix as an energy filtering barrier, leading to S enhancement.
Finally, the ZT value of 2 wt% Ag-coated SnTe at 823 K is 0.67,
which is about 60% higher than the original SnTe. Similarly, this
strategy significantly optimized the TE performance was also
observed in Bi2Te3. Zhu et al.89 successfully introduced Ru nano-
particles into a Bi2Te3 material matrix. With the increase of the Ru
content, the thermoelectric properties of Bi2Te3 are improved by
filtering low-energy carriers and causing a large range of phonon
scattering. Ultimately, the maximum ZT of 0.93 (423 K) was
measured in Bi2Te3 samples containing 1 wt% Ru, which is a
45.3% improvement compared to the pure sample. These show
that the dispersion of metallic materials as a second phase can
effectively improve the thermoelectric properties of the material
by suppressing the formation of vacancies or filtering low-energy
carriers. A summary of a recent research study on the introduction
of metal doping to form a second phase is shown in Table 1.
In addition, the introduced metal nanoparticles can react
with certain ions in the matrix to generate compounds that act

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Table 1 Summary of the typical introduction of metal doping to form a introduction of metallic Fe and their thermoelectric properties.
second phase90–105 A combination of SEM and XRD techniques showed that the
Matal Substrate ZT T (K) prepared samples contained rock salt crystal structures and
biphasic structures. Among them, metallic Fe reacts with Te in
Au PbSe 2.6 523
Ag Cu2S 1.4 773 the matrix and produces FeTe compounds, which are uniformly
Ag SnS 1.1 877 distributed in the PbTe matrix as the second phase, which is
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Ag PbTe 1.65 723 beneficial for reducing the kl values.

Pb Tl8.33Sb1.67Te6 0.46 560
Fe Ge0.96Bi0.06Te 1.65 785 3.3.2 Oxides and semiconductors. Because oxides have
Sb PbTe 1.3 673 fairly good chemical and thermal stability, they are difficult to
Bi PbS 0.89 773 react with other monomers or compounds. Oxides have low k
Bi Mg2Si0.60Sn0.4 1.2 850
Cu Bi2SeS2 1.04 773 values, and thus the introduction of oxide nanoparticles doped
Ni Bi2Te2.7Se0.3 1.1 360 to form a second phase in TE materials has received much
Ni Cu1.9S 0.9 773 attention. Similarly, a large number of research studies have
Te Cu1.8S 0.352 623
Ti NbFe1.02Sb 0.81 973 demonstrated that the introduction of oxide nanoparticles to
Sn AgSb0.98Ce0.02Se2 1.23 675 form a second phase leads to strong phonon scattering, which
Cd SnTe 1.5 900 helps to suppress kl.82,83,107–110 In contrast, the ZT value of the
thermoelectric material is improved. Fig. 5 illustrates some of
as a second phase. For example, Cao et al.106 systematically these systems’ results. Nong et al.111 successfully introduced
reported the preparation of n-type Pd1XFeXTe alloys with the the B2O3 second phase in SiGe by ball milling and spark plasma

Fig. 5 Comparison of ZT values before and after doping of different oxides into different TE materials.1–10

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Materials Chemistry Frontiers Review

sintering (SPS) processes. Although the B2O3 second phase
boundary scattered carriers, resulting in a decrease in mobility,
the increase in resistivity was acceptable. It is important that
the second phase can effectively scatter phonons, which greatly
reduces kl. Ultimately, the p-type composite achieves a maximum
ZT value of 1.47 at 873 K, which is approximately twice that of the
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the integrity of Cu2Se crystals, will react with the Cu2Se matrix
and replace Cu+ in Cu2Se to produce the CdSe second phase.
The presence of the CdSe second phase increases the k of the
material, which has a detrimental effect on the TE perfor-
mance. In this respect, however, semiconductors may play
some compensating role in improving the TE properties. This

pure SiGe alloy material. Due to the high chemical stability,
moderate band gap, and good availability of ZnO nanoparticles,
they are widely used in the second-phase modification of
nanothermal materials. For example, XIAO et al.112 prepared
Bi0.4Sb1.6Te3 materials containing ZnO nanocomplexes using
mechanical alloying and plasma-activated sintering, and ZnO
nanoparticles were distributed in the matrix as a second phase,
which effectively reduced the k values of the samples.
The introduction of metal and oxide doping, in addition
to forming a second phase on its own as in the above study,
also has the potential to react with the substrate and form a
compound second phase. For example, Cd-doped samples of
Cu2xSeCdx (x = 0, 0.0075, 0.01, and 0.02) were prepared by Lu
et al.113 using the NaCl flux method. This study showed that
doping with the right amount of Cd, although not destroying
is mainly because the introduced semiconductor nanomaterials
are less likely to react with the substrate. Moreover, it will act as a
potential energy trap between the second phase and the TE
substrate, enhancing the energy filtering effect, which may have
a more benign effect on carrier transport.
Bao et al.114 synergistically enhanced the thermoelectric
properties of commercial Bi0.5Sb1.5Te3 (BST) by introducing
amorphous Sb2S3. This resulted in an increase in the carrier
concentration in the material, and the recrystallized Sb nano-
precipitate phase formed a semi-coherent interface with the
BST matrix. An interfacial potential barrier of about 0.58 eV is
generated, which filters the low-energy carriers and leads to an
increase in S, as shown in Fig. 6a. In addition, the Sb/BST
interface leads to strong phonon scattering (Fig. 6b), which
eventually leads to a BST–0.4% Sb2S3 of about 1.31 at 330 K.

Fig. 6 (a) Band diagram of the BST–Sb interface, which shows the band alignment and the formation of the potential barrier. (b) Schematic diagram of
phonon scattering by various features introduced by incorporating Sb2S3. (c) Distribution of carriers before the formation of a PNJ: the cyan dotted line
represents the interface of the two phases with different types of electrical transport behavior. (d) Distribution of carriers after the formation of a PNJ: the
cyan dotted line frame is the charge-depletion layer and the direction of arrows shows the direction of the built-in electric field.

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Review Materials Chemistry Frontiers

The introduction of second phase doping of the semiconductor
Sb2S3 achieves a synergistic optimization of the carrier and
phonon transport properties of BST. Furthermore, since semi-
conductor materials have different n-types and p-types in
nature, PN junctions can be formed at the interface when
different types of substrates are dispersed in the same semi-
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electro-polymerization on prefabricated SWCNT membrane
electrodes and optimized the thermoelectric performance of
Ppy/SWCNT composites through interfacial engineering. The
results show that the obtained Ppy/SWCNT composite films
have a maximum power factor (PF) of 365.2  9.6 at room
temperature and a maximum ZT of 0.203  0.005.

conductor material. P-type Sb2Te3-based alloys were suitably 3.3.4 Core–shell. Numerical calculations show that the
introduced by Wang et al.115 Due to the built-in electric field core–shell composites have high thermoelectric conversion
and the formation of a charge depletion layer, the carrier efficiency because an energy barrier is created at the interface
concentration and its transport are optimized. In addition, of the core–shell composite, which scatters low-energy carriers
the PN junction provides a scattering center and leads to a when high-energy carriers pass through. Also, coherent phonon
reduction in kl. As shown in Fig. 6c and d, both n and m decrease scattering in the core–shell structure reduces the k value of the
upon increasing the Bi2Te3 content in the (Bi2Te3)0.15–(Sb2Te3)0.85 composite.133,134 This conclusion points to the direction of
composite with the introduction of a suitable PN junction, where developing high-performance thermoelectric materials. Core–
the decrease of n is mainly attributed to the binding of holes and shell is a nanoscale ordered assembly structure which is
electrons during the formation of the carrier loss layer. formed by one nanomaterial coating another nanomaterial
3.3.3 Organic–inorganic composite thermoelectric materials. through chemical bonds or other forces. Depending on the
Compared with the inorganic TE materials mentioned above, size of the formed ‘‘core–shell’’ microstructure, there are
the development of organic TE materials is relatively late. Due usually small-sized clusters and large-sized nanoparticles.
to the discovery of semiconductors and conductors in organic The large number of physical properties arising from the
materials, coupled with the advantages of their materials with chalcogenide structure of SrTiO3 makes it one of the most
a variety of types and structures, easy-to-regulate properties, widely used and studied electro-ceramic materials. Using
and the ability to prepare flexible devices, they soon received atomic simulations, Nam-Hee Park et al.135 found that Pr
widespread attention. There are many types of organic TE doping induced the generation of a core–shell structure, and
materials, including PEDOT, PANI, PPy, P3HT, PA, TCNQ, the Pr-rich grain boundaries formed in the core–shell structure
and so on. Because organic thermoelectric materials have generated a large thermoelectric power. For Pr ion defect
low s and k values, while inorganic TE materials are just the clusters, the binding energy of charge-compensated Sr vacan-
opposite.116 Therefore, compositing organic TE materials with cies is larger, and the energy increases with an increase in the
inorganic TE materials is an effective way to achieve high doping concentration, with beneficial effects on the thermal
TE performance. New interfaces can be formed between organic and electrical properties of the material. Recently, they
and inorganic materials in the composite, which significantly proposed a three-dimensional bulk core–shell material model
improve the thermoelectric performance by reducing kl, consisting of nanoscale La-doped SrTiO3 nanocubic grains and
increasing n, and producing energy filtering effects.117 In recent Nb-doped grain boundaries, which effectively form an energy
years, interfacial engineering strategies based on organic– filtering effect that enhances the PF of the grains and reduces kl.
inorganic composites have been widely used to improve the Traditional research on TE thermoelectric materials has
thermoelectric properties of composites, as shown in Table 2. focused on inorganic semiconductors, such as sulfur compounds
For example, Li et al.118 used pulse galvanostatic electro- and filled cobaltite. Liu et al.136 combined PbTe-covered amor-
polymerization (PGEP) technology to develop high-performance phous carbon sphere core–shell structures (C@PbTe) into PbSe to
polypyrrole (Ppy)/SWCNT composites by in situ pyrrole form composites and found that the samples had higher S and
lower k values compared with the matrix PbSe by thermal perfor-
mance tests. Finally, the maximum ZT value of PbSe/1 wt%
Table 2 Summary of research on some interfacial engineering strategies C@PbTe is 0.54 at 400 K, which is 13% higher than that of PbSe.
for organic–inorganic composites119–132
Cai et al.137 explored PbSe–CdSe thermoelectric materials, where a
Composite s (S cm1) S (mV K1) PF (mW m1 K2) core–shell structure of about 20 nm thick between the interface of
the matrix and the precipitated phase formed, leading to a
Ag2SeNWs/PEDOT:PSS 640 68 327.15
PEDOT NWs/Bi2Te3 776 10.4 9.06 significant reduction in kl, with ZTave reaching about 0.83 at
Sn–Se–Te NSs/PEDOT:PSS 370 58 130.3 400–923 K. Recent studies have found that metal–semiconductor
SnSe/PEDOT:PSS 326 110 394.5 core–shell structures can be used as a strategy to improve thermo-
MoSe2/PEDOT:PSS 1143 20.6 48.6
PANI/CuBO2 0.34 430 6.28 electric properties. Jin et al.138 synthesized Au–Cu2Se core–shell
PANI/TiO2 0.052 1767 16.17 nanoparticles with different thicknesses and sizes ranging from
TiO2/CNT/PANI 2183 22.9 114.5 about 38 to 53 nm. Due to the carrier energy filtering at the
SWCNTs/PANI 1440 38.9 10.4
PPy/Te 66.3  4.1 187.5  7.4 234.3  4.1 interface of the core–shell structure, S reaches 58 mV K1 at 298 K,
PPy/SWCNTs 341.6  4.7 33.2  0.7 37.6  2.3 which is 63% higher than that of the pure sample. The additional
PPy NW/graphene 36.9 16.5 1.01 phonon scattering leads to a decrease in kl and finally obtain a
PPy/TiC 160.2 10.5 1.732
CNT/P3HT 579 29.1 49.0 maximum ZT of 0.61 for the Au–Cu2Se nanocomposite at 723 K.
P3HT/SWCNTs 118  17 44.3  1.3 23.23  4.76 Fu et al.139 introduced the core–shell structure formed by the

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Materials Chemistry Frontiers
thermal diffusion of Ni nanoparticles into Yb-filled cobaltite by
thermally decomposing Ni(OAc)2 into small particles with a size of
70 nm. Due to this ‘‘core–shell’’ microstructure, the increase in m
leads to an increase in PF, and the phonons are further scattered
by the boundaries of the nanoparticles in the shell layer.
Ultimately, the maximum ZT of the sample at 723 K was 1.07
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when the Ni content was 0.2 wt%.
Organic materials, especially conjugated polymers, have
received increasing attention. This is because conjugated poly-
mers have lower k values compared to inorganic materials.
Wang et al.140 prepared well-dispersed inorganic TE materials
in a polymer matrix by a one-pot interfacial synthesis method to
produce good-performance Ag2Te-polyaniline core–shell nano-
structures. The size of the nanostructure is about 80–100 nm,
and the core consists of Ag2Te nanoparticles with a size of
10 nm. The composite nanostructures have higher S values and
lower thermal conductivity compared to pure Ag2Te and poly-
aniline powders.
4. Conclusions
Thermoelectric technology has excelled in waste heat recovery
and refrigeration. The new concept makes it possible to optimize
the mutually coupled s, S and kl in an optimally beneficial way,
gradually increasing the thermoelectric optimum ZT from the
historical threshold of 1.0 to close to 3.0. Interface engineering is
one of the main strategies and a well-designed interface can
strongly scatter phonons and low-energy carriers without sacrifi-
cing s. In this article, we focus on the effect of different solution
synthesis strategies on the nanoparticle size, morphology and
surface ligands, as well as their role at the interface. Four sections,
single atom, cluster, ligand molecule and second phase bulk
material, are selected for review depending on the size of the
multidimensional interface. Their effects on the interfacial thermo-
electric properties are also discussed separately. In addition, we
have analyzed and summarized the research on modulating the
thermoelectric properties of materials through interface engineer-
ing in recent years. The introduction of interface engineering was
eventually found to be of great benefit to both thermal and
electrical properties, leading to a substantial increase in ZT.
It should be noted, however, that this review is only a personal
summary of previously reported relevant studies and inevitably
contains omissions and an incomplete and inaccurate understand-
ing of some parts. We apologize for any possible shortcomings and
welcome valuable suggestions.
Author contributions
Conceptualization: Yue Lou and Biao Xu. Writing—original
draft: Xiaoqing Lu and Guilong Pan. Writing—review & editing:
Yue Lou, Biao Xu, and Zhan Shi.
Conflicts of interest
The authors declare no competing financial interest.
This journal is © The Royal Society of Chemistry and the Chinese Chemical Society 2023
View Article Online
Review
Acknowledgements
B. X. is thankful for the financial support from ‘‘the Funda-
mental Research Funds for the Central Universities’’, No.
30922010201, and the Key Laboratory for Soft Chemistry and
Functional Materials of the Ministry of Education, Nanjing
University of Science and Technology. Y. L. is thankful for the
financial support from the Jiangsu Provincial Innovation and
Entrepreneurship Doctor Program (JSSCBS20210215).
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