Applied Materials Today 18 (2020) 100451

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Applied Materials Today

journal homepage: www.elsevier.com/locate/apmt

The rise of conductive copper inks: challenges and perspectives

Wanli Li a,∗ , Qingqing Sun a , Lingying Li a , Jinting Jiu b , Xu-Ying Liu c ,
Masayuki Kanehara d , Takeo Minari a,∗ , Katsuaki Suganuma b
a
Center for Functional Sensor & Actuator and World Premier International Center for Materials Nanoarchitectonics, National Institute for Materials Science, 1-1 Namiki, Tsukuba,
Ibaraki, 305-0044, Japan
b
The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka, 567-0047, Japan
c
School of Materials Science and Engineering, Zhengzhou University, 100 Kexue Avenue, Zhongyuan, Zhengzhou, Henan, 450001, PR China
d
C-Ink. Co., Ltd., Sojya-shi, Okayama, 719-1121, Japan

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

Article history: Conductive inks have gathered increasing attention in the fabrication of next-generation electronic
Received 13 May 2019 devices because of their prominent compatibility and producibility. Recently, copper (Cu) inks as the
Received in revised form 14 August 2019 new darling of conductive inks are studied extensively because Cu possesses an intrinsic high conduc-
Accepted 8 September 2019
tivity (comparable to the highest conductive metal, silver (Ag)) but an ultralow cost (about 1% the cost of
Ag) with abundant reserves. However, the low resistance of Cu towards oxidation results in three issues,
Keywords:
in aspects of the synthesis of stable Cu inks, the fabrication of highly conductive Cu patterns, and the
Cu inks
long-term reliability of Cu-based electronic performances, which hinders the application prospect of Cu
Sintering methods
Long-term reliability
inks in the next-generation electronic devices. Herein, this review summaries the advanced develop-
Printed electronics ments of Cu inks in term of formulations, sintering methods, and long-term reliability. The mainstream
Flexible electronics strategies for avoiding oxidation and improving the stability of Cu inks and Cu patterns are described,
while the efficient sintering methods and related sintering mechanisms are analyzed. The effect of ink
formulations and sintering methods on the conductivity of Cu patterns on various substrates are also
discussed. In addition, the strategies for the improvement of long-term reliability of Cu patterns and
their application in various devices are summarized and forecasted. Finally, the challenges and future
prospects for Cu inks are involved as well.
© 2019 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Classification of conductive Cu inks and their characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Cu nanoparticle inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1. Strong stabilizing agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.2. Core-shell structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.3. Hybrid metal nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Cu precursor inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2.1. Cu salt inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2.2. Cu ion inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2.3. Cu complex inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.4. Cu oxide inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.3. Mixed Cu inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. Sintering methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1. Thermal sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

∗ Corresponding authors.
E-mail addresses: jsczlwl@outlook.com (W. Li), MINARI.Takeo@nims.go.jp
(T. Minari).

https://doi.org/10.1016/j.apmt.2019.100451
2352-9407/© 2019 Elsevier Ltd. All rights reserved.
2 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451

3.1.1. Reducing atmospheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

3.1.2. Reducing solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.1.3. Addition of pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2. Photonic sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2.1. Laser sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2.2. Intense pulsed light (IPL) sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.3. Plasma sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.4. Chemical sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4. Long-term reliability of sintered Cu patterns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.1. Oxidation of Cu patterns and anti-oxidation strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.1.1. Increasing the density of sintered Cu patterns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.1.2. Overcoating stable layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.1.3. Adding elements with high oxidation resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.2. Mechanical fatigue of flexible Cu patterns and enhancement strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.2.1. Microstructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.2.2. Adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5. Applications of Cu inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.1. Antennas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.2. TFTs and sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.3. Touch screen panels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.4. Die-attach materials for power electronic packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
6. Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

1. Introduction materials, Ag inks present both high stability and highest conduc-
tivity. For example, Ag inks formulated from particles of 4.4 nm,
Printed electronics (PE) technology, merging traditional print- stabilizing agent of carboxylic acid, and solvent of toluene were suc-
ing technologies into electronic manufacturing, has attracted cessfully sintered below 140 ◦ C and obtained sintered Ag patterns
increasing attention in the field of materials science and tech- with low resistivity of 5.8 ␮·cm [45]; what’s more, the sintering of
nology [1–7]. Compared with traditional electronic manufacturing Ag inks could even be realized at room temperature by using special
processes such as vacuum deposition [8], plating [9–11], and destabilizing agents to detach the stabilizing agent from the surface
photolithography [12,13], PE technology greatly simplifies the of nanoparticles [46]. These achievements allow us to print highly
technological process via directly printing required materials in conductive patterns on not only rigid substrates but also flexible
customized sizes and shapes [14–17]. It brings about the possibil- substrates such as polyimide (PI) [47,48], polyethylene naphthalate
ity of fabricating electronic circuits and assembly of devices in a (PEN) [49], polyethersulphone (PES) [50], polyethylene terephtha-
much faster, cost-effective, and environmentally-friendly way. In late (PET) [51], and paper [14,52]. They have been successfully used
addition, PE technology enables electronic circuits and devices to as electrodes or circuits for various electronics such as antenna [14],
be compatible with various plastic substrate materials rather than radio frequency identification device (RFID) tags [53,54], thin film
conventional hard silicon wafers or printed circuit boards [18–21]. transistors [15], light emitting devices [55], solar cells [56], sen-
It endows electronic devices with additional advantages such as sors [57,58], and touch screen panel [59]. However, it should be
light-weight, bendable, flexible, and even foldable which are highly noted that with the market expansion, the high cost and resource
demanded in the next-generation smart electronics [22,23]. PE shortage of Ag have hindered the applications in large-scale printed
technology involves three basic elements: printable materials, electronic production.
printing methods, and post-treatment methods [24]. Among them, Since Cu is much more abundant (1000 times more abundant
printable materials, including conductive, semiconducting, dielec- of Ag) and much cheaper (about 1% the cost of Ag) while possesses
tric, and insulating materials, are designed to fabricate different an intrinsic high conductivity (similar to Ag and higher than Au),
components of integrated devices, which are the foundation of recently Cu inks are attracting increasing attention and consid-
printed electronics. Especially, printable conductive materials also erable studies have demonstrated Cu inks to achieve conductive
called conductive inks are used to generate conductive patterns patterns [60–65]. For example, Cu inks formulated from particles
that are core parts of the electronic devices, showing a huge appli- of 45 nm, stabilizing agent of polyvinylpyrrolidone (PVP), and sol-
cation prospect [25]. Therefore, over the past decades, formulations vent of ethylene glycol (EG) were successfully sintered to achieve
of conductive inks have been extensively studied to print out highly resistivity of 17.2 ␮·cm at 325 ◦ C [60]; in order to accord with the
conductive and stable patterns on various substrates. plastic substrates, a lower temperature of 150 ◦ C could be used to
A large variety of conductive inks have been developed such as realize resistivity of 30.0 ␮·cm by decreasing the Cu nanoparti-
carbon nanotube inks [26–29], graphene inks [30], metal nanopar- cle size to 3.5 nm and changing the solvent and stabilizing agent to
ticle inks [4,25], metal precursor inks [3,31,32], conductive polymer propylene glycol and 1-amino-2-propanol, respectively [66]. How-
inks [33–35] and so on. It is evident that only metal inks such as gold ever, it is noteworthy that, compared with the Ag inks mentioned
(Au) [17,20], silver (Ag) [36,37], copper (Cu) [38,39], aluminum (Al) above, the required sintering temperatures of Cu inks are much
[40,41], and nickel (Ni) inks [42,43] are able to achieve high conduc- higher but the achieved conductivity is lower. It is because of the
tivity ranging from 100 to 102 ␮·cm easily because these metal higher melting point of Cu than Ag and the easy oxidation tendency
materials have a high intrinsic conductivity (Au, 2.44 ␮·cm; Ag, of Cu nanoparticles in ambient conditions [62]. Especially, the oxi-
1.59 ␮·cm; Cu, 1.68 ␮·cm; Al, 2.65 ␮·cm; Ni, 6.99 ␮·cm) and dation of Cu causes stable but undesirable oxide layers, such as
their nanoparticles can be sintered effectively to form a percolation cuprous oxide (Cu2 O) and cupric oxide (CuO) layers, which heav-
structure and realize high electrical conductivity [44]. Among these ily impede the interdiffusion of Cu atoms among Cu particles and
 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451
Fig. 1. Systematic evaluation of Cu inks based on the ink formulations, sintering
methods, and properties of sintered Cu patterns. The ink formulations and sintering
methods determine the properties of sintered Cu patterns, including microstructure,
resistivity, and long-term reliability. The choice of the sintering methods depends
on the ink formulations whereas the adjustment of ink formulations complies with
the sintering methods.
decrease the formation of percolation pathways, resulting in low
conductivity of the printed patterns [67]. Besides, there is another
problem of Cu inks that the fabricated Cu patterns reveal a vulner-
ability to atmospheric adsorbates such as water and oxygen with a
continuous degeneration of conductivity, which limits their prac-
tical applications severely [68,69]. In the past decade, numerous
efforts have been devoted to the development of stable Cu inks
and highly efficient sintering methods, in order to fabricate Cu pat-
terns at low temperatures and achieve high conductivity as well as
long-term reliability.
Although relative review papers about the achievements of
Cu chemistry and nanotechnology have been reported [62,70,71],
they mainly focused on the synthesis of Cu nanoparticles rather
than a systematic study of Cu inks for printed electronics. Thus,
in this review, the most recent researches of Cu inks are summa-
rized, including ink formulations, sintering methods, properties,
and application prospect, aiming to give a comprehensive and
intensive overview of Cu inks (Fig. 1), and promote researches and
applications of cost-effective Cu inks. In section 2, we classify the
current Cu inks according to the formulations and highlight their
strategies for the improvement of ink stability. In addition, the basic
transformation mechanisms from various Cu inks to conductive Cu
patterns and the effect of formulation on the achieved conductivity
are discussed. In section 3, we summarize the sintering methods,
sintering mechanisms, as well as effective strategies for obtaining
high conductivity of sintered Cu patterns. In section 4, we focus on
the enhancement of long-term reliability of printed Cu patterns and
highlight the latest effective strategies for improving their oxida-
tion resistance and mechanical property. In section 5, the emerging
applications of Cu-based inks in next-generation electronics are
summarized. In section 6, challenges and future prospects for Cu
inks are provided.
2. Classification of conductive Cu inks and their
characteristics
As well known, formulations of conductive inks are of great
importance because they not only determine the processability
of inks but also affect the final characterizations of the sintered
patterns. Particularly, the formulations of Cu inks require addi-
tional attention because Cu is susceptible to oxidation even at room
temperature (Fig. 2A). The oxidation of Cu increases the sintering
temperature and decreases the conductivity of sintered patterns,
hindering their application in printed electronics, especially on
3
heat-sensitive substrates such as PEN, PET, and paper. To solve the
problem of oxidation and achieve high-performance Cu patterns
by the low-temperature process, different formulations of Cu inks
have been developed during the past decade, which can be classi-
fied into three types: Cu nanoparticle inks, Cu precursor inks, and
mixed Cu inks. In this section, the main formulations of Cu inks and
their strategies for improving the stability of inks will be summa-
rized. In addition, the effect of ink formulation on the conductivity
of Cu patterns will be discussed.
2.1. Cu nanoparticle inks
Metal particles can be sintered into conductive patterns due to
the interdiffusion of atoms among adjacent particles [44], which
is the basis for the development of metal particle inks. Since
the sintering temperature of metal particles decreases with the
decrease in particle size [72], Cu nanoparticles inks are widely
studied [60,73–77]. The inks normally consist of Cu nanoparticles,
stabilizing agents, and some volatile solvents. The nanoparticles
can be synthesized by chemical methods and physical methods
[66,67,73,74,77–85]. During the synthetic process, the stabilizing
agent is added to cover the surface of Cu nanoparticles, which pre-
vents the agglomeration of the Cu nanoparticles [4,60]. In some
cases, to accommodate different printing methods, additional addi-
tives such as surface tension modifiers, humectants, and binders
are needed to adjust the viscosity, consistency, and wettability of
the inks [4]. The information of reported Cu-based nanoparticle
inks in terms of the materials, particle sizes, stabilizing/reducing
agents as well as sintering methods has been listed in Table 1. As
mentioned above, the oxidation problem of Cu is the core issue for
development of Cu inks, especially Cu nanoparticle inks because Cu
nanoparticles have high specific surface areas and active surfaces.
As shown in Table 1, three strategies have been utilized extensively
to prevent the oxidation of Cu nanoparticle inks, which can be clas-
sified into using strong stabilizing agents, core-shell structures, and
hybrid metal nanoparticles roughly.
2.1.1. Strong stabilizing agents
Strong stabilizing agents such as polyvinylpyrrolidone (PVP)
[60,67,91,108], oleic acid [39], Tergitol NP-9 [80], polyethylene
glycol 2000 (PEG-2000) [73], and oleylamine [119,121], polyally-
lamine [123] can better cover the surface of the Cu nanoparticles
and assist in postponing the oxidation process. For example, the
PVP with large molecular weight could well limit the formation of
the surface oxide layer (Fig. 2B). However, these strong stabilizing
agents normally require high sintering temperatures above 250 ◦ C
to remove or decompose them [65]. If these stabilizing agents can-
not be removed, they will act as barrier layers and hinder the
atom diffusion as well as charge transfer among Cu nanoparti-
cles, causing low conductivity of sintered Cu patterns. Recently,
strong stabilizing agents with lower decomposition temperatures
have been explored to prepare the Cu nanoparticle inks and realize
the sintering of them at lower temperatures [65,124]. For example,
carboxylic acids with shorter chain length (lactic acid, citric acid,
and alanine) were utilized as stabilizing agents for synthesizing Cu
nanoparticles [96]. These nanoparticles could be successfully sin-
tered at 200 ◦ C and yielded low resistivity of 9.1 ␮·cm. In addition,
1-amino-2-propanol could be used as stabilizing agents for synthe-
sizing Cu nanoparticles and the achieved nanoparticles could be
sintered at 150 ◦ C and realize a resistivity of 30 ␮·cm. However,
it should be noted all these stabilizing agents could only reduce
the amount of Cu nanoparticle oxidation but not completely stop
them from oxidation. The presence of the oxide layer prevents the
achievement of highly conductive Cu patterns with resistivity com-
parable to bulk resistivity [94].
4 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451

Fig. 2. (A) Thermodynamic stability phase diagram of Cu-Cu2 O-CuO system and (B) synthesized Cu nanoparticles using PVP of molecular weight 10,000 g/mol, 29,000 g/mol,
and 40,000 g/mol and the oxide layer thicknesses of Cu nanoparticles were measured to be 3.1, 2.5, and 1.6 nm, respectively. (A–B) Reproduced with permission from [67].
Copyright 2008, Wiley-VCH Verlag GmbH&Co KGaA. (C) Synthesized Cu-Ag core-shell nanoparticles. Reproduced with permission from [119]. Copyright 2015, IOP Publishing.
(D) Synthesized Cu-Ag hybrid nanoparticles. Reproduced with permission from [78]. Copyright 2016, IOP Publishing.

2.1.2. Core-shell structures
Core-shell structure is the second strategy for improving the oxi-
dation resistance of Cu nanoparticles in which an anti-antioxidant
shell blocks the contact between Cu core and oxidizing substances
[117–119,125–132]. The shell can be organic materials such as
polymers, amorphous carbon, and graphene or inorganic materi-
als such as silica and stable metals [62]. In view point of conductive
printing, highly conductive and stable metals are the best choice
for coating the Cu nanoparticles because they not only enhance the
stability but also retains the high conductivity. For example, Cu-Ag
core-shell nanoparticle inks were reported by Grouchko et al. [118]
and Lee et al. [119], in which Ag shell of about 2 nm could well
prevent oxidation of the Cu core (Fig. 2C). Cu-Ni core-shell struc-
tures were reported by Kim et al. [121]and Rathmell et al. [133]
and they speculated these structures could stabilize the Cu core
for hundreds of years. However, the large-scale synthesis of these
core-shell structural nanoparticles is still challenging.
2.1.3. Hybrid metal nanoparticles
Hybrid metal nanoparticles fabricated by physical methods are
promising for large-scale production [134–136] and beneficial for
the improvement of the oxidation resistance of nanoparticles. For
example, Kawamura et al. [79] and Kim et al. [78] fabricated Cu/Sn,
Cu/Ag, Cu/Ni, and Cu/Zn hybrid nanoparticle inks through the elec-
trical explosion of metal wires (Fig. 2D). However, compared with
core-shell structure, these hybrid metal nanoparticles can only pro-
tect Cu partially.
 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451 5

Table 1
Summary of Cu particle inks with information of particle size, stabilizing agents, substrates, sintering methods, and achieved resistivity.

Materials Size (nm) Stabilizing agent Substrate Sintering method Resistivity (␮·cm) Ref.

Cu 40-50 PVP Glass 325 ◦ C, vacuum 17.2 [60]

Cu 35-60 PVP PI 275 ◦ C, vacuum 92.0 [67]
Cu 30-65 PVP PI 200 ◦ C, formic acid 3.6 [86]
Cu 5 NA Glass/PI IPL 5.0 [87]
Cu 5 NA PI 250 ◦ C, formic acid NA [88]
Cu 7 Oleic acid BT 200 ◦ C, formic acid 4.0 [89]
Cu 20 NA Glass 200 ◦ C, H2 20.0 [90]
Cu 40 Oleic acid PI 250 ◦ C, vacuum 11.0 [39]
Cu 40.4 PVP Alumina 300 ◦ C, 5 MPa, air 86.0 [91]
Cu 30 PVP PI IPL 5.0 [92]
Cu 30 PVP PI Multi IPL 173.0 [93]
Cu 65 PVP Glass 250 ◦ C, formic acid 2.3 [94]
Cu 20-50 PVP PI IPL NA [95]
Cu 10 Lactic acid Glass 200 ◦ C, N2 9.1 [96]
Cu 50-70 NA PI Laser-808 nm NA [97]
Cu 42/108 Oleic acid Glass 200 ◦ C, H2 4.0 [98]
Cu 25 PVP PI Plasma 21.1 [99]
Cu 15-25 PVP Paper 160 ◦ C, Ar 13.4 [100]
Cu 100-120 NA Glass Laser-522 nm in air 5.3 [101]
Cu 135 PEG-2000 PI 250 ◦ C, N2 15.8 [73]
Cu - PVP PET Hydrogen plasma 15.9 [102]
Cu 3.5 1-amino-2-propanol PI 150 ◦ C, N2 30.0 [66]
Cu 45 NA PI Laser/IPL 8.9 [103]
Cu 100 Oleic acid PET IPL 51.2 [104]
Cu 130 Gelatin Glass 200 ◦ C, 3% H2 8.2 [105]
Cu <100 PVP PI IPL 7.0 [106]
Cu 50 PVP Glass/PEN Laser-532 in air NA [107]
Cu 30 PVP Glass 260 ◦ C, 5% H2 6.1 [108]
Cu ≤110 Oleic acid PET Laser-1064 nm in air 86.0 [109]
Cu Micron Ascorbic acid PET Chemical sintering 774.0 [110]
Cu 61.7 Trisodium citrate Glass 200 ◦ C, H2 7.6 [111]
Cu 3.6/64.6 L-ascorbic acid PET IPL 96.0 [65]
Cu 10 Poly (VI-co-VTS) Glass Sinter-free 1200.0 [112]
Cu 150 PVP PET IPL 44.0 [113]
Cu NA NA Glass/PET 150 ◦ C, formic acid 6.9 [114]
Cu 5 Isopropylamine Glass 250 ◦ C, H2 4.4 [115]
Cu 100-120 PGME Glass Laser-532 nm and 350 ◦ C, N2 1.8 [116]
Cu-G CS 45 NA Polymer 120 ◦ C, air NA [117]
Cu-Ag CS 42 PAAS Glass 250 ◦ C, N2 32.0 [118]
Cu-Ag CS 13.5 Oleylamine Glass 350 ◦ C, N2 12.0 [119]
Cu-Ag CS 13.5 TMAH Glass 350 ◦ C 13.7 [120]
Cu-Ni CS 56/147 Oleylamine PI IPL - [121]
Cu-Cu10Sn3 CS 20-60 Oleic acid PET IPL 16.0 [122]
Cu/Ag H 63/21 PVP PES 175 ◦ C, vacuum 38.6 [50]
Cu/Ni H 10-80 - Glass 200 ◦ C, H2 599.0 [79]
Cu/Ag H NA PVP PI IPL 4.1 [78]

Noted: G = graphene; CS = core shell; H = hybrid; PGME = propyleneglycol methyl ether; PAAS = polyacrylic acid sodium salt; TMAH = tetramethylammonium hydroxide;
BT = bismaleimide triazine; IPL = intense pulsed light, N2 =nitrogen; H2 =hydrogen; Ar = argon.

2.2. Cu precursor inks
Cu precursor inks have been developed to avoid the oxidation
problem of Cu inks during preparation and storage [137–139]. They
could be made from precursors such as organic Cu salts, inorganic
Cu salts, and Cu oxides so on with solvents/ligands/reducing agents
and additional additives, as shown in Table 2. Since the Cu exists
in their oxidized form, they can maintain long-term stability at
ambient conditions. During the post-treatment, these Cu precursor
inks can transform into pure metal patterns by thermal decomposi-
tion or chemical reduction processes [61,64,140,141]. Cu precursor
inks are sometimes called metal-organic decomposition (MOD) ink,
Cu salt inks, Cu ion inks, Cu ion complex inks, Cu complex inks,
or Cu oxide inks so on, which is confusing for the beginners. In
order to understand the difference among various Cu precursor
inks, we try to reclassify them into Cu salt inks [61,139], Cu ion
inks [141,142], Cu complex inks [64,69,138,140,143–146], and Cu
oxide inks [147,148] according to the precursor elements in the
inks (Fig. 3).
2.2.1. Cu salt inks
The precursor elements of Cu salt inks are Cu salt particles that
are not soluble in the solvents (Fig. 3A). For example, the Cu salt
ink fabricated by mixing Cu(II) neodecanoate and Cu(II) hydroxide
nanoparticles in terpineol could be easily printed and provide Cu
patterns with a low resistivity of 5.4 ␮·cm after thermal sintering
at 250 ◦ C for 20 min in a 3% H2 atmosphere [61]. Recently, Cu salt
particles with lower decomposition temperatures were explored
to fabricated Cu salt inks, such as Cu (II) nitrate hydroxide (thermal
decomposition temperature of 236–280 ◦ C) [149] and Cu (II) for-
mate particles (thermal decomposition temperature below 200 ◦ C)
[139]. However, the sintering temperatures of these Cu salt inks are
still too high for most plastic substrates and sometimes the use of
reducing atmospheres is uneconomic. In addition, the uniformity
6 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451

Table 2
Summary of Cu precursor inks with information of precursor materials, solvent/ stabilizing agent/ligand/reducing agent, substrate, post-treatment, and achieved resistivity.

Precursor Solvent/stabilizing agent/reducing agent/ligand Substrate Post-treatment Resistivity (␮·cm) Ref.

Cu(II) neodecanoate and Cu(II) hydroxide Terpineol Glass 250 ◦ C, 3% H2 10.0 [61]
Cu(II) formate DPM, Disperbyk 180 NA 200 ◦ C, N2 3.6 [139]
Cu(II) nitrate hydroxide Water and monosaccharide Glass IPL 125.0 [149]
Cu(II) formate DPM, isopropanol, Disperbyk 180 Glass 250 ◦ C, 1260 PSI NA [150]
Cu(II) citrate Water, sodium borohydride Paper Chemical sintering 55.5 [141]
Cu(II) glycolate Glycol Glass 250 ◦ C, N2 23.0 [151]
Cu(II) nitrate Water, PVP, and PEG PC Laser-808 nm in air NA [142]
Cu ions Formic acid, citric acid, and amine water PI 250 2 43.7 [152]
Cu(II) formate n-octyl amine Glass 140 ◦ C, N2 20.0 [153]
Cu(II) formate Hexylamine Glass 250 ◦ C, formic acid 5.2 [138]
Cu ions Formic acid, acetic acid, and ammonium hydroxide PI 200 ◦ C, H2 20.0 [154]
Cu(II) formate Octylamine and dibutylamine Glass 140 ◦ C, N2 5.0 [155]
Cu(II) formate Diethanolamine Glass IPL 56.0 [156]
Cu(II) hydroxide Ammonium hydroxide, formic acid, citric acid, PVP PET/PI IPL 5.3 [157]
Cu(II) formate AMP, octylamine Glass 350 ◦ C, N2 9.5 [140]
Cu(II) formate DEA-1, 2-PD 180 ◦ C, air NA [158]
Cu(II) formate Hexylamine Glass 200 ◦ C, N2 454.0 [146]
Cu(II) formate AMP Glass 190 ◦ C, N2 10.5 [64]
Cu(II) formate AMP, octylamine, glycerol Glass 350 ◦ C in air 17.0 [159]
Cu(II) formate Hexylamine, AMP PI pulsed ultraviolet NA [160]
laser beam
Cu(II) formate 3-butyl-pyridine, 2-ethyl-1hexylamine PET 135 ◦ C, N2 13.9 [161]
Cu(II) formate AMP PEN Argon and nitrogen 7.3 [162]
plasma treatment
Cu ions formic acid, acetic acid, and ammonium hydroxide PET hydrogen plasma 3.2 [163]
Cu(II) formate Butylamine and octylamine PET 160 ◦ C, vacuum 23.0 [164]
Cu(II) formate 1,2-diaminopropane Glass 180 ◦ C, air 18.0 [165]
Cu ions Formic acid, acetic acid, and ammonium hydroxide PI IPL 2.3 [166]
Cu(II) formate and Ag(I) ␤-ketocarboxylate 2-ethylhexylamine PET 100 ◦ C, N2 28.0 [167]
Cu(II) sulfate and Cu(II) formate Glyoxylic acid and methylamine PI Laser-1060 nm and 5.0 [168]
electroless plating
Cu(II) hydroxide DEA-1, 2-PD, and formic acid Glass 160 ◦ C, N2 238.0 [169]
Cu(II) formate 2-ethylhexylamine PI LT-IPL 3.6 [69]
Cu2 O Tergitol NP-9 Glass IPL 94.0 [80]
CuO PVP, EG Glass/PI Near-infrared laser 31.0 [170]
CuO NA PET IPL 9.0 [171]
CuO NA Paper IPL 3.1 [172]
CuO NA PET IPL 6.5 [147]
CuO EG Glass Laser-532 nm 9.5 [173]
Cu nitride EG Glass IPL NA [174]

Noted: DPM = Dipropylene glycol monomethyl ether; AMP = 2-amino-2-methyl-1-propanol; DEA-1, 2-PD = 3-diethylamino-1,2-propanediol; EG = Ethylene glycol;
IPL = intense pulsed light.

Fig. 3. Schematic of the main formulation of Cu precursor inks: (A) salt inks, (B) Cu ion inks, (C) Cu complex inks, and (D) Cu oxide inks, highlighting the precursor elements
of various Cu precursor inks.

of the printed Cu salt patterns is influenced by the particle size of
Cu salt and their dispersibility in the solvent [149,175].
2.2.2. Cu ion inks
The precursor elements of Cu ion inks are Cu ions that result
from the dissolution of Cu salt in various solvents (Fig. 3B). For
example, Cu (II) glycolate was dissolved in glycol to prepare Cu
ion inks and the low resistivity of 23.0 ␮·cm was achieved after
thermal sintering at 250 ◦ C for 60 min in N2 [151]. In addition, Cu
(II) nitrate was used as precursor and dissolved in the water con-
taining reducing agent of PVP and PEG to form Cu ion inks [142].
The PVP and PEG used as reducing agents could transform Cu ions
into metallic Cu during the laser sintering process. Compared with
Cu salt inks, Cu ion inks are particle-free, thus they are more suit-
able for various printing methods. However, the transformation of
Cu ion inks to metallic Cu also requires high temperatures/energy
and sometimes reducing agents.
 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451 7

2.2.3. Cu complex inks ing atmospheres [179], laser sintering [170] or intense pulsed
Recently, low-temperature and self-reducible Cu complex inks light (IPL) sintering [148] with suitable organic matters that can
have attracted increasing attention [64,140,153,155,156]. They are decompose to create reducing agents. The detail information about
normally made from the complexation reaction of Cu salts and sintering methods and sintering mechanisms will be discussed in
amine-based solvents (Fig. 3C). The amine solvents in the inks act as section 3.
not only solvents but also coordination ligands to form the Cu com-
plex [176]. Currently, a large variety of formulations of Cu salts and
2.3. Mixed Cu inks
amine solvents have been studied. Cu salts that have been studied
include Cu (II) acetate, Cu (II) oleate and Cu (II) formate [156,177].
Recently, mixed Cu inks are proposed (Table 3), including Cu
Among them, Cu (II) formate is deemed to the best because of
nanoparticle-large Cu particle/flake inks [180,181], Cu precursor-
its low thermal decomposition temperature, high reducing abil-
Cu particle/flake inks [182–184], Cu precursor-carbon nanotube
ity of formate, and less organic residuals after sintering [138,156].
(CNT) inks [137,185], and so on. The addition of materials such
Amine solvents that have been studied include ammonia [152,163],
as large Cu particles/flakes or CNT to Cu nanoparticle inks or Cu
various primary, secondary amines [164,178], and some tertiary
precursor inks can affect their sintering behaviors and improve the
amines [158]. The effect of amine solvents on the Cu complex inks
properties of sintered Cu patterns.
is much complicated. Take the primary amines and Cu (II) formate
Mixed Cu inks of large Cu particles (2 ␮m) and Cu nanoparticle
as an example: the complexation reaction between Cu (II) formate
(20–50 nm) were studied by Joo et al. [180], in which the achieved
and primary amine is as follows, where R indicates alkyl chain.
resistivity of sintered patterns (80.0 ␮·cm) was much lower than
Cu(HCOO)2 +2R-NH2 = Cu(HCOO)2 (R-NH2 )2 (1) those achieved by using only Cu nanoparticle inks (210.0 ␮·cm)
or only Cu large particle inks (246.0 ␮·cm). This is because the
When the Cu complex is formed, the electrons from the amino
patterns fabricated from the mixed inks tend to have a denser
group of the ligand are donated to the Cu(II) center through a
packaging density, smaller pores, and less cracks than those fab-
ligand-to-metal charge transfer process, resulting in the partial
ricated from the Cu nanoparticle inks and the Cu large particle inks
reduction of the Cu(II) center [140]. Therefore, the ligand carboxyl
[180,181,186–190]. The best mass ratio between large Cu particles
groups (−COOH) of Cu complex are more easily released than those
and Cu nanoparticles is related to their sizes and shapes, which can
of neat Cu (II) formate (Fig. 4A). With the increase of temperature,
be calculated by some mathematic models [50,191,192]. However,
the dissociation of amine from Cu complex happens subsequently
it should be noted the oxidation of Cu nanoparticles during the
accompanied by an endothermic process (Fig. 4B). The final decom-
preparation of the mixed Cu ink is hardly avoided which increases
position temperature of Cu complex is about 45–75 ◦ C lower than
the sintering temperature or requires a reducing atmosphere.
that of neat Cu (II) formate [140,164]. The proposed decomposition
To solve this oxidation problem, mixed Cu inks of Cu parti-
of Cu complex is presented in Fig. 4C, in which the configuration of
cles/flakes and Cu complexes were developed [38,68,182,183,193].
Cu complex resulted from octahedral to square planar and finally
As shown in Fig. 6A, the decomposition of Cu complexes could
to metallic Cu [64].
in-situ create fresh and fine Cu nanoparticles. These nanoparticles
In addition, amine solvents acted as stabilizing ligands can influ-
tend to cover the surface of added Cu particles/flakes and realize
ence the growth of Cu particles in the decomposition process of Cu
the bonding between them at low temperatures [182,183]. On the
complex inks and therefore affect the conductivity of sintered Cu
other hand, the addition of Cu particles/flakes into Cu complex inks
patterns at low temperatures. As shown in Fig. 5A, amines with low
functioned as nucleation sites could easily control the decompo-
boiling temperatures or weak coordination strengths to Cu center
sition process of Cu complexes (nucleation and growth of Cu) and
are easier to release and cannot block the growth and aggregation
realize Cu patterns with uniform microstructures as well as high-
of Cu particles, resulting in a porous structure with wide particle
qualitative surface morphologies [182,183,194]. Also, the thickness
size distribution while amines with high boiling temperatures can
of sintered Cu patterns is increased effectively by the addition of
restrain the growth of Cu particles and yield patterns with nar-
Cu particles/flakes, which is beneficial for reducing the resistance
row particle size distributions. Besides, the concentration of amine
of sintered Cu patterns [182,195]. Therefore, low resistivity of 11.3
also affects the microstructure and resistivity of sintered Cu pat-
and 88.0 ␮ cm were easily achieved from these mixed inks at
terns [138,146]. Fig. 5B show the resistivity of the sintered patterns
140 and even 100 ◦ C, respectively [182,193]. The ratio between the
fabricated from various Cu complex inks. As seen, primary amines
added Cu particles/flakes and Cu complex affects the performance
(such as EtHex and Octyl) with an intermediate boiling point near
of Cu patterns [182,193].
165–175 ◦ C appear to be ideal for achieving highly conductive Cu
Later, mixed Cu inks of Cu precursors and carbon nanotubes
patterns (6.2 and 7.1 ␮ cm, respectively) at low temperatures
(CNTs) were also developed [137,185]. Compared with the patterns
(140 ◦ C) because they can well control the growth of Cu parti-
obtained from pure Cu complex inks, patterns obtained from Cu
cles and be removed easily. On the other hand, using blended
complex-CNT inks have more uniform microstructure and thick-
amines with different alkyl chain lengths (such as butylamine-
ness because the CNTs could provide heterogeneous nucleation
octylamine [164] or octylamine-dibutylamine [155]) can balance
sites for the decomposition of Cu complex (Fig. 6B). Besides, the dis-
the nucleation and growth speed during the decomposition of the
tinct light absorption property of CNTs improves the efficiency of
Cu complex and produce a lower resistivity (5.0 ␮ cm). Although
photonic sintering technology [137]. However, compared with pure
Cu complex inks have been widely studied to achieve highly con-
Cu, the conductivity of CNTs is low, which increase the resistance
ductive Cu patterns on plastic substrates at low temperatures, they
of Cu patterns.
still have a big issue: the low Cu loading in the inks (< 20%), which
contributes to only very thin Cu patterns unless multi-printing is
used. 3. Sintering methods

2.2.4. Cu oxide inks
Stable Cu oxide nanoparticles including Cu2 O and CuO can also
be used as precursor for fabrication of Cu inks [147,170–173]
(Fig. 3D), but these Cu inks require a special sintering process to
form conductive patterns, such as thermal sintering under reduc-
After printing conductive inks onto substrates and drying, a sin-
tering process is normally required for the inks to acquire specific
electronic properties. In case of Cu nanoparticle inks, during the
sintering, the stabilizing agents, solvents, and additional organics
are removed first and then the interdiffusion and Ostwald ripening
8 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451

Fig. 4. (A) Mass spectrometry and (B) thermogravimetric analysis-differential scanning calorimetry of the decomposition of Cuf-octyl complex and Cuf. Octyl = Octylamine and
Cuf = Cu (II) formate anhydrous. (A–B) Reproduced with permission from [164]. Copyright 2016, American Chemical Society. (C) A suggested mechanism for the decomposition
of the Cu complex. Reproduced with permission from [64]. Copyright 2015, Royal Society of Chemistry.

phenomena can occur among the unprotected Cu nanoparticles,
which leads to the bonding or coalescence and realizes electrical
conductivity [44]. In case of Cu precursor inks, the formation of
conductive pathways here is attributed to nucleation and growth
of Cu during the decomposition and reduction of Cu precursors as
well as the sintering afterward (the whole process is also called
sintering in this work) [167]. The conductivity of printed Cu pat-
terns is determined by not only the bonding of each Cu particle
(also called necking) and microstructure of printed Cu patterns
(density and porosity) but also the phase composition (Cu, Cu2 O,
and CuO) and organic residuals. A variety of sintering methods
have been studied to increase the conductivity of Cu patterns,
including thermal sintering, photonic sintering, plasma sintering,
chemical sintering, and so on. In this section, the feature and
mechanism of sintering methods and the effective strategies for
obtaining highly conductive Cu patterns will be summarized and
discussed.
3.1. Thermal sintering
Thermal sintering is a whole heat treatment of conductive inks
and substrates by a hot plate, oven, or tube furnace, which has
been widely used in the field of printed electronics due to the low-
cost and user-friendly equipment. The sintering temperature of Cu
nanoparticle inks is depended on the organic system and the size
of Cu particles (see section 2.1) while that of Cu precursor inks is
mainly depended on their decomposition temperatures (see sec-
tion 2.2). Normally, a higher sintering temperature can improve
the sintering efficiency of various Cu inks. Besides the sintering
temperature, reducing atmospheres, reducing solvents, and pres-
sure also affect the sintering efficiency of Cu inks and therefore the
conductivity of Cu patterns.
3.1.1. Reducing atmospheres
Since Cu is easily oxidized during the thermal sintering process,
normally inert atmospheres (such as N2 , Ar), vacuum, or reducing
 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451 9

Fig. 5. (A) Schematic illustration of the nucleation and sintering behaviors of Cu complexes containing low boiling point amines, weakly coordinating amines, or high boiling
point amines and (B) the resistivity of Cu patterns formed by sintering various Cu complex inks. Reproduced with permission from [178]. Copyright 2018, Royal Society of
Chemistry.

Table 3
Summary of mixed Cu inks with information of mixed materials, solvent/ligand/reducing agent, substrate, post-treatment, and achieved resistivity.

Materials Stabilizing/solvent/ ligand/reducing agent Substrate Sintering method Resistivity (␮· cm) Ref.

Cu nano/microparticle PVP, DG PI IPL 80.0 [180]

Cu nanoparticle/flake Oxalic acid PI 150 ◦ C, air 55.0 [188]
Cu nanoparticle/flake Polymeric matrix PET IPL 28.0 [196]
Nanoparticle/Cu nanowire PVP, DG PI IPL 22.8 [197]
Cu nanoparticle/MWCNT PVP, DG PI IPL 7.9 [198]
Cu nanoparticle/silver nitrate DG, PVP, formic acid Glass IPL 200.0 [199]
Cu particle/Sn particle PVP PET IPL NA [200]
Cu particle/Ag complex 2-ethylhexylamine PI 140 ◦ C, air and IPL 3.4 [201]
Cu formate/Cu particle Terpineol PI 275 ◦ C, N2 13.0 [63]
Cu formate/Cu particle Terpineol PI Laser-355 nm, N2 18.6 [202]
Cu formate/CNT DPM PI IPL NA [137]
Cu nitrate/nanoparticle PVP, DG PI IPL 27.3 [203]
Cu complex/Cu particle 1-amino-2-propanol Alumina 100 ◦ C, N2 900.0 [183]
Cu complex/Cu particle AMP Glass 140 ◦ C, N2 11.3 [182]
Cu complex/Cu particle AMP PET 140 ◦ C, N2 and IPL 26.5 [38]
Cu Complex/Cu flake 1-amino-2-propanol Paper 150 ◦ C, N2 110.0 [143]
Cu complex/Cu flake AMP Glass 200 ◦ C, N2 30.0 [195]
Cu complex/Cu particle 1-amino-2-propanol Alumina 100 ◦ C, N2 88.0 [193]
Cu complex/Cu particle AMP PI IPL 5.8 [68]
Cu complex/CNT AMP, n - octylamine PET 140 ◦ C, N2 25.3 [185]

Noted: AMP = 2-amino-2-methyl-1-propanol; DG = diethylene glycol; IPL = intense pulsed light.

atmospheres (formic acid and H2 ) are required to protect them from
being oxidized (Tables 1–3). It is found that reducing atmospheres
not only prevent Cu from oxidation but also decrease the sintering
temperatures of Cu inks. Lee et al. [86] reported that formic acid
could decrease the sintering temperature of Cu nanoparticle inks
to 200 ◦ C and realize sintered Cu patterns with a resistivity of 3.6
␮·cm, only two times that of bulk Cu. In contrast, thermal sinter-
ing under vacuum yielded a high resistivity of 27.8 ␮·cm even at
275 ◦ C [67]. Kim et al. [89] confirmed the function of formic acid
and found the gaseous mixture of 70% formic acid and 30% alcohol
to be the best for sintering of Cu nanoparticle inks. The reducing
atmospheres were considered to drive the reduction in Cu oxides as
well as the decomposition of capping organics, therefore increasing
the sintering efficiency of Cu inks [114]. Woo et al. [94] compared
the reduction abilities of various saturated monocarboxylic (formic,
acetic, propionic, butyric) and found that the acids with shorter
hydrocarbon chains performed better in reducing the surface Cu
oxides. H2 atmospheres were also studied for thermal sintering of
Cu nanoparticle inks but they showed less efficiency than formic
acid [89].
10 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451

Fig. 6. (A) Schematic illustration of the nucleation and sintering behaviors of pure Cu complex inks and Cu complex-Cu particle inks. Reproduced with permission from
[182]. Copyright 2016, Royal Society of Chemistry. (B) Macroscopic and microscopic structure of the pattern fabricated from pure Cu complex inks and Cu complex-CNT inks.
Reproduced with permission from [185]. Copyright 2018, WILEY - VCH Verlag GmbH & Co. KGaA.

3.1.2. Reducing solvents
Besides the reducing atmospheres, the addition of reducing sol-
vents in Cu inks is another approach to remove surface Cu oxides
and protect Cu particles from oxidation during the sintering pro-
cess. For example, reductive polyethylene glycol (PEG) used as the
solvent in Cu/CuO particle ink could significantly reduce CuO into
Cu and improve the sintering of Cu inks [204]. Reductive polyol
solvents such as glycerol could also improve the sintering of Cu pre-
cursor inks. After sintering at 350 ◦ C even in air, Cu patterns with
a low resistivity of 17.0 ␮·cm could be obtained [159]. Reductive
ascorbic acid (AA) gives the similar result but enables the sintering
the of Cu particles at a lower temperature [205]. Kanzaki et al. [188]
studied the effect of dicarboxylic acid (oxalic acid, malonic acid, and
succinic acid) on the sintering of Cu inks and found oxalic acid was
the most effective in suppressing Cu oxidation. It is likely that the
large dissociation constants of oxalic acids coordinate to the Cu
surface and result in the dissolution of surface Cu oxide quickly.
Because of this high antioxidant effect, the developed Cu nanopar-
ticle ink could be well sintered even in air (55.0 ␮·cm, sintered at
150 ◦ C for 10 s).
3.1.3. Addition of pressure
In addition, use of pressure during thermal sintering is another
approach to improve the conductivity of metal patterns because the
pressure increases the contact area of metal particles and increase
the rate of sintering, resulting in a uniform and dense microstruc-
ture [206]. For example, Rosen et al. [150] used a combination of
heat and pressure for sintering a Cu(II) formate particle ink. They
found that the application of pressure enables the formation of a
dense Cu patterns with a resistivity as low as 5.3 ␮·cm while with-
out the pressure, the achieved Cu patterns have a greater degree of
porosity with a high resistivity. However, the addition of pressure
increases the complexity of application.
Although much effort has been made, the thermal sintering of
Cu nanoparticle inks either requires a high sintering temperature
or yields low conductivity. Reducing atmospheres and solvents can
effectively improve the sintering of Cu nanoparticle inks, but the
 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451
sintering temperature for highly conductive Cu patterns is still as
high as 150 ◦ C. Cu complex inks are suitable for low-temperature
sintering, but the required temperature of about 140 ◦ C is still a little
bit high for plastic substrates with low glass transition tempera-
tures. In addition, the long duration time of thermal sintering is not
compatible with roll-to-roll (R2R) fabrication for mass production.
3.2. Photonic sintering
Photonic sintering is that utilizing light radiation ranging
between the ultra-violet (UV) and near infra-red (IR) range to
realize the sintering of inks. By matching the emission spectrum
of the light source with the absorption spectrum of the print-
able materials, the light will be mainly absorbed by the printable
materials to realize the selective sintering with less damage of
substrates. Photonic sintering includes IR sintering [207,208], UV
sintering [209,210], laser sintering [211,212], and intense pulsed
light (IPL) sintering [213–215]. These sintering methods have been
successfully used to realize the sintering of various conductive
inks [215–221]. For detailed information of these photonic sin-
tering methods, the reader is referred to the reported literatures
[44,222,223], and here only the important conclusions related to
Cu inks are summarized. Among these photonic sintering meth-
ods, laser sintering and IPL sintering offer very rapid and intense
energy sintering processes within several milliseconds (IR and UV
sintering methods normally need a longer time ranging from sev-
eral seconds to tens of minutes) so that the oxidation of Cu can be
minimized. In addition, since the sintering time is short and the
energy is mainly absorbed by the Cu inks, the heat transfer to the
substrates is limited [103]. Therefore, laser sintering and IPL sin-
tering are widely adopted in the sintering of Cu inks for printed
flexible electronics. It should be noted that until now much work
is still in academic research, not yet realized in the industry.
3.2.1. Laser sintering
Laser provides a highly dense energy with a small spot size (usu-
ally in dozens of micron diameter or smaller [44,107]) through
the coherent light emission on a fixed wavelength, thus it can be
employed to sinter various Cu inks at a fast working speed without
oxidation even in air (Fig. 7A). Yu et al. [101] used a laser of 532 nm
wavelength to sinter Cu nanoparticle inks and achieved resistivity
of patterns as low as 5.3 ␮·cm, which was much better than that
achieved by thermal sintering at 300 ◦ C. Later, the same group uti-
lized a laser with 355 nm wavelength to sinter Cu precursor inks
and achieved Cu patterns with resistivity of 21.0 ␮·cm and with-
out oxidation [224]. The change of wavelength from 532 nm to
355 nm is determined by the absorption spectrum of Cu precur-
sor inks. The absorption of nanoparticle inks is in the visible region
while precursor inks show strong absorption bands below 400 nm
[44]. The mechanism of laser sintering of Cu precursor inks in air
has been reported by Ohishi et al. [168,225]: the high energy and
heat supplied by the laser can decompose the Cu precursors rapidly
and since the in-situ formed Cu particles are minute, they melt and
grow into larger stable Cu particles before they are oxidized.
Laser is also used to sinter CuO nanoparticle inks [170,173,226].
For example, Kang et al. [170] reported that CuO nanoparticles
dispersed in ethylene glycol could be instantaneously reduced
to Cu nanoparticles and sintered to form conductive patterns by
laser irradiation (Fig. 7B). The reduction of CuO nanoparticles is
attributed to the reducing agents: acetaldehyde, which is generated
by laser-induced dehydration of ethylene glycol. On the other hand,
laser can be used to sinter metal nanowires network [216,227].
Especially, the surface plasmonic effect induced by a wavelength
below 550 nm enables a localized heat generation at the junc-
tions of each Cu nanowire that realizes the selective sintering of
Cu nanowires (Fig. 7C). In addition, laser sintering is very suitable
11
to be used to fabricate high resolution of printed patterns because
of the small laser spot [107,109,170,212].
However, it should be noted the behavior of laser sintering is
limited by the thermal resistance of the plastic substrates. The
minimum resistivity of the sintered Cu patterns was inversely
proportional to the thermal resistance of the plastic substrates
(Fig. 7D). A high level of laser power will damage the substrates
and cause the delamination between substrates and printed Cu
electrodes [109]. In addition, it is difficult to use laser sintering for
large areas, unless continually scanning the small laser spot over
the area.
3.2.2. Intense pulsed light (IPL) sintering
Compared with other photonic sintering methods, intense
pulsed light (IPL) sintering (also called flash light sintering) employs
a wider range of light wavelength from 200 to 1000 nm even above
rather than a fixed wavelength (Fig. 8A). Therefore, IPL sintering
can provide a high-energy density for sintering of conductive inks,
which is similar to laser sintering. Compared with laser sintering,
IPL sintering has another advantage that it can be used for large-
scale sintering depended on the size of the xenon lamp. Therefore,
IPL sintering is regarded as one of the most promising sintering
methods to achieve highly conductive Cu patterns on a large scale
[229].
Kim et al. [87] firstly used IPL to sinter Cu nanoparticle inks
and found that IPL could sinter the Cu nanoparticles in 2 ms. The
achieved resistivity of Cu patterns is 5.0 ␮·cm which is one third
of that of the thermally sintered Cu nanoparticle ink (17.2 ␮·cm,
sintered at 325 ◦ C for 1 h in vacuum) [60]. Later, the same group
found that IPL process could reduce the Cu (I) oxide layer of Cu
nanoparticles with the help of PVP, realizing conductive and pure
Cu patterns in air [92,217]. The in-situ reduction of the Cu oxide
layer is attributed to the intermediate alcohol or acid resulting from
photo-degradation of PVP [214,217,230,231], as shown in Fig. 8B.
Besides PVP, some commonly used organic matters such as ethy-
lene glycol [80], hexadecylamine (HDA) [232], and octadecylamine
(ODA) [233] can also function as reducing agents during the IPL
sintering.
With the help of reducing agents, IPL sintering of CuO nanopar-
ticle inks has been successfully realized [147,148,171,172,234]. For
example, Rager et al. [234] reported that during the IPL sintering of
CuO nanoparticle inks, reducing agents resulting from the photo-
degradation of ethylene glycol could reduce the CuO nanoparticles
to Cu, which was similar to the mechanism of laser sintering of CuO
nanoparticle inks [170]. Paglia et al. [147] further found that the
CuO nanoparticles were reduced to Cu2 O first and then to metallic
Cu (Fig. 8C). By optimizing the energy of the IPL, the CuO nanopar-
ticle inks could be totally reduced and sintered to Cu patterns with
a conductivity of more than 25% of the value of bulk Cu. Addition-
ally, Rager et al. [234] found that a pre-sintering drying of CuO inks
for 24 h provided significant enhancement in both conductivity and
environmental stability of IPL-sintered Cu patterns. A pre-sintering
drying step allows excess solvents to diffuse through the porous
structure of the silica-coated PET substrate which not only prevents
delamination but also minimizes pore formation caused by rapid
“explosive” evaporation. Later, Ö hlund et al. [172] used papers,
which is coated with active layers of porous calcium carbonate
and acidic mesoporous absorption, as substrates to improve the
effectiveness and reliability of the IPL sintering of CuO inks. The
whole processing is realizable within 5 ms, yielding a resistivity of
3.1 ␮·cm, corresponding to more than 50% of the conductivity of
bulk Cu.
IPL has also been used to sinter Cu complex inks. The light
absorbed by Cu will create high temperatures that induce the rapid
decomposition, reduction, and sintering of Cu complex inks. Oh
et al. [157] reported that with the increase of IPL energy to above
12 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451

Fig. 7. (A) Schematic illustration of laser sintering and (B) conversion of CuO nanoparticles into Cu pattern by photochemical reduction and photonic sintering. (A–B)
Reproduced with permission from [170]. Copyright 2011, American Chemical Society. (C) Plasmonic laser nanowelding of Cu NWs. Reproduced with permission from [228].
Copyright 2014, WILEY-VCH Verlag GmbH & Co. KGaA. (D) Minimum resistivities obtained from Cu electrodes on glass, PI, PEN, and PET substrates. Reproduced with
permission from [109]. Copyright 2016, American Chemical Society.

40 J cm−2 , the Cu precursor ink is successfully reduced to pure
Cu and form highly conductive Cu patterns with resistivity of 5.3
␮·cm (Fig. 9A). The effect of the type of Cu carboxylates (Cu(II)
formate, acetate, and oleate) on the IPL sintering of Cu complex
inks was studied by Araki et al. [156]. However, it should be noted
that the high energy of the IPL instantly applied to the Cu complex
inks induces the release of a large volume of gases in a very short
period of time [137,156,157]. This causes a porous structure of sin-
tered Cu patterns and makes them uneven. To solve this problem,
Li et al. [69] developed a two-step sintering method consisting of
low-temperature precuring followed by IPL sintering (LT-IPL). The
low-temperature pre-curing at 140 ◦ C for 10 min allows the decom-
position of the Cu complex inks to form Cu nanoparticles in a mild
and ordered way and then the IPL sintering with low energy den-
sity derive the rapid densification of Cu nanoparticles to form dense
and robust Cu patterns. By this method, highly dense and uniform
Cu patterns were achieved with a high conductivity of 50% bulk Cu
(Fig. 9B).
However, it is noteworthy that similar to laser sintering of Cu
inks, almost all highly conductive Cu patterns achieved by IPL sin-
 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451
Fig. 8. (A) Schematic of the IPL system and emission spectrum at various applied voltages. Reproduced with permission from [222]. Copyright 2017, Royal Society of Chemistry.
(B) Schematics of the photo-degradation of PVP, resulting in alcohol or acid. Reproduced with permission from [217]. (C) Transformation of CuO to Cu during IPL sintering.
Reproduced with permission from [147]. Copyright 2015, American Chemical Society.
tering were only accomplished on heat-resistant substrates such
as glass and PI substrates. This indicates that the required energy
for the sintering of Cu inks is still high which induces high tem-
peratures between Cu and substrates that beyond glass transition
or melting temperatures of heat-sensitive substrates such as PEN
and PET. The requirement of high energy is likely attributed to the
presence of oxides on the surface of Cu particles [104], precursors
with high decomposition temperatures [38,203], or a large amount
of organic matters [69,156]. Besides a threshold energy for the den-
sification of Cu nanoparticles, additional energy should be supplied
to realize the photochemical reduction of the Cu oxides to the pure
Cu, to decompose the Cu precursors having high decomposition
temperatures, and to remove the organic matters such as solvent,
stabilizing and reducing agents. This increases the total energy of
IPL for the sintering of Cu inks and results in a critical limitation
in using vulnerable plastic substrates [104]. In addition, the thick-
ness of Cu patterns that can be generated through IPL sintering is
limited due to the surface-localized sintering process [235]. There-
fore, further optimization of Cu ink formulations as well as sintering
processes should be studied in the future.
3.3. Plasma sintering
Plasma sintering is using the ionized gas, which is consisted of
electrons, ions, and neutrals in in fundamental and excited states, to
bombard the printable materials and realize the sintering of print-
able materials [44,236]. The chemical nature of plasma is related
to the feed gas that is used for the generation of plasma [44]. For
example, plasma can acquire reducing, inert or oxidizing abilities
13
by using H2 , N2 , or O2 respectively. Therefore, plasma can be used to
realize the decomposition/reduction of metal precursor, evapora-
tion of organic materials, and sintering of nanoparticles. One basic
advantage of plasma sintering in printed electronics is keeping the
temperature as low as possible [44], which therefore can be used
to realize conductive patterns on various heat-sensitive substrates
such as PET, PEN, and paper.
Gao et al. [102] reported on the use of H2 plasma to sinter submi-
cron Cu particle inks on PET substrates. They found the resistivity
of achieved Cu patterns is dependent on the plasma model (normal
plasma etching vs reactive ion etching (RIE)), power, and treatment
time. Conductive Cu patterns with a resistivity of 15.9 ␮·cm was
achieved at 200 W for 10 min. Furthermore, they confirmed that the
temperature of the substrate treated with the RIE model plasma
only had a slight increase up to 75 ◦ C, which was far lower than
the damage temperature of many polymer substrates. The sinter-
ing of Cu particle at such low temperature is attributed to the very
clean and active surface of Cu particles induced by high energy reac-
tive plasma species bombardment and therefore the surface atomic
diffusion. Kwon et al. [163] reported on the use of H2 plasma to
sinter Cu complex inks on paper substrates. H2 plasma can easily
reduce the Cu complex ink to pure metal Cu and realize the sin-
tering. Compared with conventional thermal sintering in H2 , the
plasma treated Cu pattern shows a denser microstructure with a
lower resistivity of 3.2 ␮·cm. These properties can be attributed
to the fact that the much greater sintering potential energy of
the plasma causes lower levels of nucleation and increased grain
growth, resulting in the patterns with high dense and uniform
microstructures. Knapp et al. [176] did a similar research and con-
14 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451
Fig. 9. (A) Microstructures and electric resistivities of Cu complex inks after IPL sintering at different energy densities. Reproduced with permission from [157]. Copyright
2013, American Chemical Society. (B) Microstructures, thickness, and electric resistivities of Cu complex inks after LT-IPL sintering with different energy densities. Reproduced
with permission from [69]. Copyright 2018, WILEY-VCH Verlag GmbH & Co. KGaA.
firmed that H2 plasma can reduce the Cu precursor inks to pure
metal Cu and achieve conductive patterns at temperatures below
70 ◦ C.
Besides reductive plasmas, inert plasmas are able to convert
Cu precursor inks to conductive Cu patterns. Farraj et al. [162]
reported on the N2 and Ar plasma-induced decomposition of Cu
complex inks for the formation of highly conductive Cu patterns
(Fig. 10A). The transformation of the Cu complex into metallic Cu
was studied by X-ray photoelectron spectroscopy (XPS) measure-
ments (Fig. 10B). By optimizing the parameters (gas flow, process
time, and power) of plasma sintering, Cu patterns with a low resis-
tivity of 7.3 ␮·cm was achieved. The possible mechanism involves
the decomposition of COOH- and NH2 - species by high energy
argon ion bombardment during plasma exposure, leaving the metal
species behind, which is similar to the plasma-induced decompo-
sition of the Ag nitrate [237].
Although plasma sintering can realize the sintering of various Cu
inks at low temperatures, it is hard to realize the selective sinter-
ing. During the plasma sintering, the substrates without patterns
are also damaged by ion bombardment [162]. In addition, plasma
sintering is difficultly achievable in R2R processing because of a
reduced pressure and a rather long processing times ranging from
several minutes to hours.
3.4. Chemical sintering
The approach of chemical sintering describes the introduction
of sintering agents such as destabilizing agents or reducing agents
to realize the sintering of printed inks [36,44,46]. It has been widely
used to transform various Ag and Au inks into their conductive
counterpart while few research activities have been done about Cu
inks. Bidoki et al. [238] investigated the adaptability between dif-
ferent Cu precursor inks (Cu sulfate and Cu nitrate) and reducing
agents (sodium dithionite, sodium thiosulfate, zinc formaldehyde
sulfoxylate, and ascorbic acid) by ink-jet printing of aqueous Cu
precursor inks and reducing agent consecutively onto the substrate.
It is found that ascorbic acid can transform Cu precursor into solid
particles, but the resulting pattern is not conductive due to the rapid
oxidation of the formed particles. The authors hoped this prob-
lem might be overcome by working under an inert atmosphere. Li
et al. [141] reported on another chemical sintering system to real-
ize conductive Cu patterns on paper substrates. Aqueous Cu citrate
solutions used as Cu precursors were firstly ink-jet printed onto the
paper substrate and then sodium borohydride (NaBH4 ) dissolved in
0.5 M NaOH solution was deposited to reduce the Cu precursor to
metal Cu. The partial oxidation of the formed Cu during chemical
sintering could be suppressed by multiple printing cycles. However,
the achieved conductivity of Cu patterns was still as low as 3.3% that
of bulk Cu due to the poor microstructure. Recently, Sheng et al.
[110] reported the chemical sintering of Cu particles. The authors
used a large amount of aqueous solution of ascorbic acid (AA) to
adequately clean the surface of Cu particles for 6 h and after that
the fresh Cu particles could be easily bonded with each other by the
rearrangement of nearby Cu atoms (also called surface diffusion).
Conductive Cu patterns could be easily achieved on various sub-
strates including paper and heat-sensitive PET and PEN substrates,
but the resistivity is much higher (774.0 ␮·cm) than that of bulk
Cu, indicating the low sintering efficient of this method.
4. Long-term reliability of sintered Cu patterns
The long-term reliability of sintered Cu patterns is signifi-
cantly important because it determines whether these sintered Cu
patterns can go into practical applications [69,213,239]. For the
sintered Cu patterns, besides the high conductivity, they need to
have high oxidation resistance and robust mechanical property,
both of which allow them to work stably under various application
conditions. Therefore, in this section, the strategies for improv-
 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451 15

Fig. 10. (A) Scheme of the printing and plasma exposure process resulting in formation of continuous Cu films and (B) XPS analysis of Cu 2p, carbon-hydrogen bond, and
carbon-oxygen bond with an increase in the duration of the plasma treatment. Reproduced with permission from [162]. Copyright 2017, American Chemical Society.

ing the reliability of sintered Cu patterns will be summarized and
discussed.
4.1. Oxidation of Cu patterns and anti-oxidation strategies
Oxidation is the key problem for application of Cu inks, which
should be minimized or eradicated from the synthesis stage to the
application stage. Many novel Cu inks and sintering methods have
been developed to realize high conductivity of Cu patterns without
oxidation on various substrates (as described above). However, the
oxidation occurs again in the sintered Cu patterns, which decreases
their conductivity and hinders their practical applications. Nor-
mally, aging tests in high temperatures and high humidity in air
are used to evaluate the environmental reliability of sintered Cu
patterns. The oxidation behaviors of Cu pattern and degeneration
of conductivity are recorded with the increase of aging time [68]. It
should be noted that sintered Cu patterns normally have a porous
structure composed of many Cu particles with a low density, which
is different from the dense Cu bulk structure. Fig.11 shows the dia-
grammatic drawing of oxidation behaviors of the Cu film with a
bulk structure and the sintered Cu pattern with a porous structure.
In the case of Cu patterns with a bulk structure, the oxidation of
Cu occurs at the outer surface and then diffuse into the inner side
slowly (Fig. 11A). In contrast, in case of sintered Cu patterns with
a porous structure, many Cu particles in the inner side of patterns
directly contact with oxygen/water (Fig. 11B). The oxidation occurs
in both outer and inner sides of sintered Cu patterns simultane-
ously, accelerating the oxidation and deterioration. To date, three
strategies have been proposed to improve the environmental reli-
ability of sintered Cu patterns, including 1) increasing the density
of sintered Cu patters, 2) overcoating stable layers, and 3) adding
elements with high oxidation resistance.
4.1.1. Increasing the density of sintered Cu patterns
A dense structure of Cu patterns is preferred. Paglia et al. [147]
reported on sintered Cu patterns with a dense surface layer. A two-
layer deposition method was utilized in which the printed ink of the
second layer penetrated into the pores of the underlying sintered
patterns and form a denser surface. This dense surface prevents
the penetration of O2 into the underlying layer and limits the oxi-
dation of the metallic Cu phase. However, the two-layer printing
process is complicated for mass production. Hwang et al. [198]
found the addition of CNT to the Cu particle inks could decrease the
number and size of pores in the IPL-sintered Cu patterns and there-
fore increase the oxidation resistance of sintered patterns. Li et al.
[69] further modified the microstructure of sintered Cu patterns
by low-temperature pre-curing and IPL densification enhancement
treatment. The resulting fully dense structure of Cu patterns enable
them to prevent the permeation of oxygen and water into the inner
side of the Cu patterns, thereby greatly improving their oxidation
resistance and maintaining a stable resistance even after 1000 h in
85 ◦ C-85% RH. Later, the same group [68] reported the effects of
Cu particle size on the oxidation resistance of sintered Cu patterns.
They found that the long-term reliability of sintered Cu patterns is
attributed to not only the intrinsic oxidation of Cu to Cu2 O/CuO but
also the degradation of their microstructures.
4.1.2. Overcoating stable layers
Overcoating Cu patterns with anti-oxidation materials or
embedding Cu patterns into polymer could greatly improve the
oxidation resistance of sintered Cu patterns [233,240,241]. For
example, Hong et al. [242] presented an overcoating structure made
of a polyimide and SiOx thin film that effectively prevents the
penetration of oxygen and moisture into the Cu nanowire-based
conductors. This structure enables Cu nanowire-based conductors
16 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451
Fig. 11. Diagrammatic drawing of oxidation behaviors of (A) the Cu film with a bulk structure and (B) the sintered Cu pattern with a porous structure.
to have excellent stability not only at high temperatures but also in
underwater, acidic chemical, and abrasive conditions. However, the
overcoating method is complicated and time-consuming. Akiyama
et al. [243] found that residual products from 2-amino-2ethyl-1,3-
propanediol (AEP) ligands could coat the surface of sintered Cu
patterns and form a protective coating to efficiently protect the sin-
tered Cu patterns from oxidation. However, the residual products
cause the decrease of conductivity.
4.1.3. Adding elements with high oxidation resistance
Introduction of elements having high oxidation resistance such
as Au, Ag, Ni, Sn into sintered Cu patterns is the third method
[126,127,244–246]. Core-shell structures (mentioned in section
2.1.2) are often used to improve the oxidation resistance of Cu parti-
cles/nanowires as well as the sintered Cu patterns [247]. Grouchko
et al. [118] reported that conductive patterns fabricated form Cu-
Ag core-shell nanoparticles kept high oxidation resistance in air,
and no oxidation was found even after several months in ambient
conditions. Kim et al. [121] reported that conductive patterns fabri-
cated from Cu-Ni core-shell nanoparticles kept highly stable (R/R0 <
2) even after 30 days of aging in 85 ◦ C-85% RH test. Core-shell struc-
ture is also used to improve the reliability of Cu nanowire-based
patterns. For example, Niu et al. [248] reported that the resistance
of Cu-Au core-shell nanowire-based patterns maintained stable in
80 ◦ C-80% RH test for at least 700 h.
On the other hand, Kawamura et al. [79] evaluated the reliabil-
ity of sintered patterns from Cu/Sn, Cu/Ag, Cu/Ni, and Cu/Zn hybrid
nanoparticle inks in 85 ◦ C-85% RH test. It is found that the resistiv-
ity of the Cu-30Zn and pure Cu patterns increased rapidly while the
increase in the resistivity of the Cu-1Sn, Cu-5Ag, Cu-5Ni, and Cu-
30Ni patterns were relatively slower. After 24 h, 4.3, 0.54, 13 and
11% of the initial conductivity was retained for the Cu-1Sn, Cu-5Ag,
Cu-5Ni, and Cu-30Ni patterns, respectively. The long-term reliabil-
ity of these patterns expected to be further improved by optimize
their sintering methods. Chung et al. [78] utilized IPL to sinter Cu/Ag
hybrid nanoparticle inks and enable the Cu/Ag hybrid patterns to
retain stable even at 100 ◦ C. Yim et al. [199] reported a similar
research but replaced the Ag nanoparticles by Ag nitrate. During the
IPL sintering, the decomposition of Ag nitrate can create metal Ag to
improve the oxidation resistance of achieved patterns. However, it
should be noted that the decomposition of Ag nitrate increases the
porosity of sintered patterns and deteriorate their microstructures.
Recently, Li et al. [201] reported on dense Cu-Ag alloy patterns fab-
ricated from Cu-Ag nanoparticles core- shell structures (Fig. 12).
The resulting dense Cu-Ag alloy patterns have ultrahigh oxidation
resistance even up to 180 ◦ C in air. In addition, these Cu-Ag alloy
patterns can maintain a stable resistance (R/R0 <1.5) even after 1000
bending cycles at 220 ◦ C [249].
4.2. Mechanical fatigue of flexible Cu patterns and enhancement
strategies
Mechanical property is another key point to evaluate the
reliability of sintered metal patterns, especially for the flexible
metal patterns [69,250–253]. Sintered Cu patterns are required to
maintain their electrical performance during different mechani-
cal deformations. For example, during the bending or stretchable
tests, the change of resistance of Cu patterns should be as small
as possible, which is crucial for the stably work of the whole elec-
tronic system. Normally, adhesion tests and fatigue tests including
inner/outer bending and folding are used to evaluate the mechani-
cal properties of sintered Cu patterns [122]. It should be noted that
the electrical conduction of printed Cu electrodes can be realized
even by weak necking or slight contact. However, these necking
and contact cannot provide a robust mechanical property because
they are easily broken under repetitively mechanical test.
4.2.1. Microstructures
Li et al. [69] investigated the effect of microstructure on the
mechanical property (e.g., bending fatigue) of Cu patterns and
found that a dense structure with robust bonding between Cu
particles can resist against crack formation and propagation and
therefore improve their bending fatigue property. In case of Cu
patterns with a porous structure, high stress concentrated at small
neck-like junctions causing a brittle fracture of the patterns. Joo
et al. [197] reported on the effect of the addition of Cu nanowires
on the mechanical property of sintered Cu patterns. It is found
that Cu inks with 5 wt.% Cu nanowires greatly enhance the den-
sity and flexibility of sintered Cu patterns. However, the oxidation
and self-aggregation of Cu nanowires have made it difficult to fab-
ricate uniform patterns on a large scale. Later, the same group [198]
replaced Cu nanowires to CNT and found that 0.5 wt.% CNTs with
the length of 200 ␮m shows the best enhancement of flexibility in
sintered patterns. The obtained patterns show enhanced bending
fatigue property because the CNTs distribute the stress concen-
trated at neck-like junctions in the porous structure and retard the
crack propagation among Cu particles.
4.2.2. Adhesion
In general, sintered Cu patterns cannot adhere to polymer
substrates because there are no Cu-polymer interactions. A poor
adhesion between the sintered Cu patterns and substrates cause
interfacial delamination and decrease the flexibility of the fab-
 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451
Fig. 12. Dense Cu-Ag alloy patterns with ultrahigh oxidation resistance. Reproduced with permission from [201]. Copyright 2017, American Chemical Society.
ricated devices. Lee et al. [154] and Jeon et al. [254] utilized
a silane coupling agent to improve the adhesion between sin-
tered Cu patterns and PI substrates because oxane bonds could
be formed between sintered Cu patterns and PI substrates. It is
found that Cu patterns containing 3 wt.% silane coupling agent
exhibit the highest adhesion strength as well as the low resis-
tivity. The resistance change of Cu patterns without silane was
much higher (R/R0 = 4.1) than that of Cu patterns with 3 wt.% silane
(R/R0 = 1.2) after 1000 cycles bending. Wu et al. [110] reported
that residual ascorbic acid (AA) in the Cu patterns could improve
the adhesion between Cu and the polymer substrate because AA
includes a lactone ring with two hydroxyl groups that resembles
L-3,4-dihydroxyphenylalanine (L-DOPA) and enables mussels to
attach to almost all types of substrates. Akiyama et al. [243] further
reported that the presence of residual products from 2-amino-
2ethyl-1,3-propanediol (AEP) ligands strengthened the adhesion
between the sintered Cu patterns and the PET substrate. The AEP
related oxidative products could serve as effective binders, pre-
venting neck-like junctions from being broken and retarding linear
crack propagation during bending in the patterns. In addition, it is
reported that the addition of 3-aminopropyl triethoxysilane [159],
poly(3-glycidoxypropyl)trimethoxysilane [174], and bisphenol-F
type BEF170 epoxy resin [255] can increase the adhesion between
Cu patterns and flexible substrates. However, it should be noted
that the addition of these adhesion agents inevitably decreases
the conductivity of sintered Cu patterns because these adhesion
agents are non-conductive. On the other hand, it is reported that
IPL sintering can improve the adhesion between sintered patterns
and various plastic substrates by local soften effect [38,256]. The
IPL selectively sinters the metal particles/nanowires and simulta-
neously soften or even melt the interface between the metal and
substrates that helps in achieving metal patterns with high con-
ductivity and strong adhesion [38,113,220].
In conclusion, the mechanical property of sintered Cu patterns
is determined by their microstructures and the adhesion between
sintered Cu patterns and substrates. A robust bonding between
sintered Cu particles is beneficial for the enhancement of conduc-
tivity but more importantly, it can greatly increase the mechanical
property of sintered patterns by resisting against crack formation
and propagation. On the other hand, a good adhesion prevents the
delamination of sintered Cu patterns from substrates and improve
their mechanical reliability.
5. Applications of Cu inks
In recent years, Cu inks have been attempted to apply in
various electronics such as flexible circuits [182,201], heater
[170,247], antenna [38,73,102,257], sensors [65], thin film tran-
sistors (TFTs) [104,258], solar cells [259], transparent conductive
17
electrodes (TCEs) [107,109,122,200], flexible touch screen panel
[107,109,122], and power electronic packaging [186,205]. Even
though they are in the exploratory stage, the progress in this field
is obvious. Here, we will briefly introduce some applications of Cu
inks in the field of next-generation electronics.
5.1. Antennas
A future Internet of Things (IoT) society requires mass
production of high-performance flexible antennas for wireless
communication devices. Cu inks as one of the most promising mate-
rials can be used to realize Cu patterns on plastic substrates that
can be used as flexible antennas [38,73,102,257]. For example, Li
et al. [38] reported on V-shaped dipole Cu antenna patterns on PI,
PEN and PET substrates (Fig. 13A). The Cu antenna were 30 mm in
length and 5 mm in width with an angle of about 30◦ . As shown in
Fig.13B, the return losses (S11) of Cu antennas on PI, PEN and PET
substrates were -52 dB, -35 dB and-18 dB, respectively, which are
sensitive enough for practical application. Therefore, they are very
promising in the field of wireless communication devices.
5.2. TFTs and sensors
Sintered Cu patterns can also be used as electrodes for flexible
TFTs and sensors. Norita et al. [258] and Oh et al. [104] reported
on IPL-sintered Cu patterns used for source and drain electrodes in
TFTs (Fig. 14A). The fabricated TFTs showed good mobility levels of
0.13 cm2 /Vs and 1.4 cm2 / Vs respectively. Ankireddy et al. [65] and
Rager et al. [234] reported on IPL-sintered Cu electrodes for chem-
ical sensors and resistive temperature sensors, respectively. When
exposed to different concentrations of ethanol vapors, the resis-
tance of chemical sensors increased to 300 times higher than the
initial value, exhibiting an excellent response (Fig. 14B) [65]. The
resistance of resistive temperature sensors showed a linear depen-
dence with respect to the temperature [234]. In addition, sintered
Cu patterns can be used as flexible electrodes for electrophysio-
logical monitoring of electromyograms, electrocardiograms, and
electrooculograms (Fig. 14C).
5.3. Touch screen panels
In addition, sintered Cu patterns on plastic substrates can be
used as TCEs for the flexible touch screen panels [107,109,122,200].
As shown in Fig. 15A, Cu inks were first deposited onto PEN sub-
strates by a blade coating method and then selectively sintered by
laser to form designed Cu mesh patterns. After washing away the
non-sintered Cu inks by dichlorobenzene or deionized water, Cu
mesh-based TCEs with high conductivity and high transmittance
were achieved (Fig. 15B). Subsequently, these Cu mesh patterns
18 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451

Fig. 13. (A) Photographs of V-shaped dipole Cu antennas on various substrates and (B) return losses of Cu antennas. Reproduced with permission from [38]. Copyright 2017,
Royal Society of Chemistry.

Fig. 14. Sintered Cu patterns used as electrodes for flexible TFTs and sensors. (A) A Flexible TFT using sintered Cu patterns as source and drain electrodes. Reproduced with
permission from [104]. Copyright 2015, Royal Society of Chemistry. (B) A chemical sensor and its response as a function of vapor pressure of ethanol. Reproduced with
permission from [65]. Copyright 2017, Royal Society of Chemistry. (C) Electrophysiological monitoring based on sintered Cu patterns. Reproduced with permission from
[166]. Copyright 2018, American Chemical Society.

were used for flexible touch screen panels, as shown in Fig. 15C
and D.
5.4. Die-attach materials for power electronic packaging
On the other hand, Cu inks can be used as novel die-attach
materials for power electronic packaging [186,187,260,261]. High-
power semiconductors such as silicon carbide (SiC) and gallium
nitride (GaN), with wide band gaps, are expected to operate at
temperatures above 200 ◦ C, even 350 ◦ C, which beyond the appli-
cation temperatures of the most traditional die-attach materials.
Die-attach materials based on metallic particles such as Ag parti-
cles and Cu particles have been proved to be promising alternatives
because of their low processing temperatures and high working
temperatures [262–266]. For example, Liu et al. [267] reported
on formic acid-treated Cu nanoparticle inks that could be used to
obtain high strength and highly conductive Cu joints at a low tem-
perature of 260 ◦ C (Fig. 16). However, a high pressure of 10 MPa was
necessary, which complicated the application process heavily. Gao
et al. [205] reported on novel Cu particle inks with self-reduction
and self-protection characteristics for die attachment of power
semiconductors under N2 . Sintered Cu joints with high bonding
strengths of 25 MPa can be achieved at 300 ◦ C with a low pressure
of 0.4 MPa.
Even though Cu inks have been successfully applied in a variety
of electronics and show high performances, the long-term relia-
bility of these fabricated electronics is rarely reported. Sintered
Cu patterns are easily oxidized (as mentioned above) even under
room temperature, which complicates the practical applications of
Cu ink-based electronics. In the further, the long-term reliability
 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451 19

Fig. 15. (A) Laser-sintered Cu mesh-based TCEs for the flexible touch screen panel; (B) digital images of Cu mesh-based TCEs; (C) and (D) flexible touch panels with the Cu
mesh pattern on PEN film. (A) and (D) Reproduced with permission from [109]. Copyright 2016, American Chemical Society. (B) and (C) Reproduced with permission from
[107]. Copyright 2016, American Chemical Society.

Fig. 16. Schematic diagram of the formation of highly conductive and high-strength Cu joints between high-power chips and substrates. Reproduced with permission from
[267]. Copyright 2016, American Chemical Society.

of Cu ink -based electronics should be evaluated first and special
packing methods are required to improve the reliability of these
electronics.
6. Summary and outlook
As summarized above, there is remarkable scientific and tech-
nological progress in the development of Cu inks during the past
decade. Many effective strategies, in terms of ink formulations,
20 W. Li, Q. Sun, L. Li et al. / Applied Materials Today 18 (2020) 100451
sintering methods, and reliability enhancement, have been put
forward to solve the oxidation problem of Cu and realize highly
conductive and stable Cu patterns on various substrates. How-
ever, despite significant progress, there are several issues to be
addressed before the wide application of cost-effective Cu inks in
next-generation electronic devices.
It is still highly challenging to achieve highly conductive and sta-
ble Cu patterns on heat-sensitive substrates such as PEN and PET,
let alone high efficiency and large-scale production. Plasma sin-
tering is very suitable to low-temperature sintering of various Cu
inks and achieves highly conductive Cu patterns on heat-sensitive
substrates, but how to improve the sintering efficiency is a main
research direction; photonic sintering is a highly efficient and selec-
tive sintering method for mass manufacturing, but the necessary
photonic energy of various Cu inks needs to be tailored by the
further optimization of Cu ink formulations as well as sintering
processes.
In addition, Cu patterns with high resolution will be necessary
due to the miniaturization of printed electronics. Laser sintering
might be a suitable method; however, the complicated process and
material-waste are not suitable for wide and universal applications.
New methods based on ink formulations and printing techniques
should be paid more attention.
At last, the oxidation problem of Cu should be taken into con-
sideration not only during the preparation and storage of Cu inks
but also during the application of sintered Cu patterns. Now highly
conductive Cu patterns without oxidation can be achieved easily,
but how to keep long-term reliability of these patterns is still a
big problem. In addition, until now, there is no test standard for
evaluating the reliability of sintered conductive patterns.
We expect that the further study of cost-effective Cu inks
will promote the explosive development and application of next-
generation smart electronics, which are likely to result in a big
impact on our society.
Acknowledgements
This work was financially supported by a Grant-In-Aid for Scien-
tific Research (No. 26286040 and 17H02769) from the Ministry of
Education, Culture, Sport, Science, and Technology of Japan and the
New Energy and Industrial Technology Development Organization
(NEDO), Japan.
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