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because copper is a very abundant material, possesses high conductivity (after silver), and it has huge
potential to replace expensive conductive inks made of silver, graphene, CNTs, etc. The other reason
behind focussing on copper is its properties, such as ductility, malleability, thermal dissipation activity,
anti-microbial nature, etc. In this review, we have listed some of the best methods of synthesizing
DOI: 10.1039/c5ra08205f
copper conductive inks and their usage in various printing techniques. Dierent methods of sintering for
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1. Introduction
Nanotechnology is a rapidly developing advance and its products are extremely useful in all elds, in view of their small size
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P. S. Karthik is a research
student at the CSIR-Indian
Institute of Chemical Technology, Hyderabad, India, in the
group of Dr Surya Prakash
Singh. He has completed his
Bachelor and Master degrees at
Jawaharlal Nehru Technological
University, Hyderabad, India.
His research interests are
focussed on synthesizing carbon
nanomaterials using various
techniques and applying them in
the eld of solar energy. He is also focussed on fabricating solar
cells using dierent light absorbing materials. He has published
three research papers in the eld of Nanotechnology.
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Scheme 1
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Fig. 1
Fig. 2 UV-visible absorption spectra of copper nanoparticles with 2ethoxyethanol as a function of PVP concentration, acting as a stabilizing agent (reprinted with permission from ref. 8).
The non-linear optical properties were measured using the Zscan technique.9,10 It was used to determine the magnitude8 of
the non-linear refractive index (n2) and non-linear absorption
coecient (a2). The obtained results imply that n2 doesnt
correspond to the third order non-linear response and hence
the susceptibility totally corresponds to a2, as shown in Fig. 3.
Fig. 3
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Fig. 4
ref. 8).
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Fig. 5 TEM image of copper nanoparticles prepared in (a) N2, (b) air
and (c) O2 (reprinted with permission from ref. 13).
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Fig. 6
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Fig. 9 TEM image of oblate-shaped copper NPs, HRTEM image displaying a layer of PVP, and SAED pattern indicating the polycrystalline
structure (reprinted with permission from ref. 16).
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Fig. 12 TEM image with a scale bar of 200 nm displaying particles with
uniform shape and size (reprinted with permission from ref. 20).
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Fig. 13 TEM results of copper nanoparticles synthesized at dierent temperatures: (i) 150 C, (ii) 160 C, (iii) 190 C and (iv) 210 C (reprinted with
permission from ref. 21).
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Fig. 14 TEM analysis of copper nanoparticles with dierent size distributions obtained with dierent concentrations of lactic acid: (a) 0 mol l1,
(b) 2.8 mol l1, (c) 5.6 mol l1, (d) 8.4 mol l1, (e) 11.2 mol l1 and (f) 14 mol l1 (reprinted with permission from ref. 22).
Fig. 15 TEM analysis of copper particles stabilized by dierent carboxylic acids of concentration 14 mol l1: (a) acetic acid, (b) glycolic acid, (c)
glycine, (d) alanine, (e) citric acid (reprinted with permission from ref. 22).
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TEM images of PEG-stabilized copper nanoparticles with PEG : copper: (a) 6 : 1, (b) 7 : 1 and (c) 9 : 1 and PEG-stabilized copper
nanoparticles (reprinted with permission from ref. 23).
Fig. 17
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Polyol synthesis
Fig. 19 TEM results displaying the copper nanoparticles stabilized in PAAm/AAm with dierent molar ratios of PAAm/Cu: (a) 2.00, (b) 97.0{AAm/
Cu}, (c) 0.11 and (d) 0.46 (reprinted with permission from ref. 24).
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Fig. 20 XPS spectra of Cu nanoparticles: (a) Cu 2p3/2, (b) C 1 s and (c) O 1 s (reprinted with permission from ref. 29).
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SEM images of Cu NPs synthesized as a function of concentration of reducing agent: (a) 12.75 mmol, (b) 17.53 mmol and (c) 19.13
mmol (reprinted with permission from ref. 29).
Fig. 21
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HR-TEM image of synthesized Cu NP displaying an amorphous layer twin boundary, with a scale bar of 5 nm. SAED pattern of a
single particle is inset (reprinted with permission from ref. 29).
Fig. 25
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Fig. 26 (a) Solutions of copper oxide to pure copper nanoparticles, (b) UV-visible spectra, (c) UV-vis spectrum of Cu2O sample (reprinted with
permission from ref. 32).
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Fig. 27 (a) STEM image of the copper nanocolloid. (b) Particle size distribution interpreted through STEM analysis. (c) Particle size analysis
through DLS (reprinted with permission from ref. 32).
and (b) after coating with octanethiol (reprinted with permission from
ref. 35).
Photochemical synthesis
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Colour change of precursor solution after homogenizing copper nitrate with NaOH with various molar ratios: (a) no NaOH addition, (b)
1 : 1, (c) 2 : 1, (d) 3 : 1, (e) 4 : 1 and (f) 5 : 1 (reprinted with permission from ref. 36).
Fig. 29
Fig. 30 Morphology of the copper powders synthesized from various molar ratios of NaOH : Cu(NO3)2 at reux at 140 C (reprinted with
permission from ref. 36).
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Fig. 31 Morphology of copper colloids prepared using a NaOH : Cu(NO2)3 molar ratio of 3 : 1 at various reaction temperatures: (a) 120 C, (b)
140 C and (c) 160 C (reprinted with permission from ref. 36).
Fig. 34
Fig. 32
Fig. 35 SEM images of aged copper colloid: (a) copper dried on silicon
and (b) copper lm deposited on quartz substrate (reprinted with
permission from ref. 39).
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Fig. 36 TEM analysis of copper nanoparticles irradiated with ultraviolet radiation; the obtained particle size is less than 100 nm (reprinted
with permission from ref. 42).
Microwave-assisted synthesis
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Fig. 39 (a) TEM image of copper nanoparticles prepared using standard procedure. (b) SAED pattern of the obtained copper (reprinted
with permission from ref. 48).
Fig. 41 FESEM images of copper particles: (a) low magnication and
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(a & d) TEM images of powder and colloid, respectively, (b & e) HR-TEM of powder and colloid, respectively, and (c & f) SAED pattern of
powder and colloid, respectively (reprinted with permission from ref. 49).
Fig. 42
2.5
Fig. 43
Electrochemical synthesis
Electrochemical synthesis of nano-structured materials is achieved by passing an electric current between a cathode and
anode separated by an electrolyte. Electrochemical synthesis
has advantages of low cost, simple handling, exibility, low
contamination and no requirement of vacuum.5 Electrochemical synthesis has been used for the fabrication of nanostructured energy harvesting materials, nanosheets, nanorods,
etc.51,52 The electrochemical deposition methods have been
proved to be highly productive and readily adoptable. Electrodeposition of nanomaterials allows the formation of thin layers
with the added advantage of kinetic control. Some parameters
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Fig. 44
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SEM images of copper thin lms obtained by electrodepositing at varying pH: (a) 4.0, (b) 5.0 and (c) 9.0 (reprinted with permission from
ref. 53).
Fig. 45
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The potentiostatic electrochemical metal deposition technique was used for synthesizing Cu nanowires by Narayan
et al.,55 using ITO-coated glass as a working electrode, Pt wire as
a counter electrode and Ag/AgCl as a reference electrode in the
electrochemical cell. The electrolyte used was a solution of
CuSO4$5H2O in KCl, and the pH of the solution was maintained
at 4.5 by addition of dilute sulfuric acid. The schematic of the
cell used in this experiment is illustrated in Fig. 50.
SEM was performed on the obtained Cu nanowires grown on
the ITO glass substrate. The diameters of the obtained nanowires ranged from 110 nm to 140 nm. SEM analysis also showed
greater uniformity and higher yield, as shown in Fig. 51 and 52,
when compared to the conventional AAO template technique.
The TEM images of the Cu nanowires are shown in Fig. 53, with
the SAED pattern shown in Fig. 54.
2.6
Fig. 49 TEM image showing the presence of amorphous and crystalline structures (reprinted with permission from ref. 54).
Fig. 51 SEM images of Cu nanowires synthesized using the electrochemical process (reprinted with permission from ref. 55).
Fig. 50 Schematic of the electrochemical cell used to synthesize Cu nanowires (reprinted with permission from ref. 54).
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Fig. 55 TEM image of copper nanoparticles stabilized in starch solution (reprinted with permission from ref. 58).
range of 2070 nm, as shown by the TEM analysis (Fig. 55). They
noticed that the size of the copper nanoparticle depends on the
concentration of the copper precursor. Nayak et al.59 synthesized
copper nanoparticles by reducing the copper precursor (CuSO4)
with ginger (Zingiber ocinale) extract and proved that the
obtained nanoparticles exhibit an anti-microbial eect. Gajera
et al. synthesized copper nanoparticles using the extract of nag
champa (Artabotrys odoratissimus)60 leaf broth to reduce copper
sulphate pentahydrate. The size of the obtained nanoparticles
was 135 nm at an average rate.
2.7
Fig. 53
ref. 55).
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the copper patterns were tested, as shown in Fig. 60, at oxidation and reduction temperatures.
Kim et al.73 synthesized a copper nanoparticle ink for inkjet
printing by dispersing the organic-coated copper nanoparticles
in non-polar solvent at 40% by weight. The organic coating was
used to prevent the copper nanoparticles from agglomerating.
The synthesized copper nanoparticle ink was patternized using
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Fig. 61 SEM of printed electrode (a) before sintering and (b) after
sintering (reprinted with permission from ref. 73).
Fig.
Fig. 62 SEM images of pattern printed (a) 5 times, (b) 10 times and (c) 20 times (reprinted with permission from ref. 73).
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Fig. 64
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Surface proles of copper patterns printed (a) 5 times, (b) 10 times and (c) 20 times (reprinted with permission from ref. 73).
Table 1
Sample
Synthesis atmosphere
Thickness
Resistivity
Sample 1
Sample 2
Bulk Cu
Hydrogen
Hydrogen + argon
N.A.
1.8 0.3 mm
5.3 0.3 mm
N.A.
1.74 107 Um
9.68 107 Um
1.67 108 Um
Fig. 66 Schematic representation of the fabrication of copper nanoparticle ink and sintering by means of intense light pulses (reprinted
with permission from ref. 75).
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Fig. 71 Topographical images of copper patterns (a) before sintering, (b) sintered with energy of 576 J cm2 and (c) sintered with energy of 1723
J cm2 (reprinted with permission from ref. 75).
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Fig. 73
Fig. 74
Schematic representation of copper pattern drawn on the PI substrate before and after sintering (reprinted with permission from ref. 76).
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Fig. 76 Sheet resistance change analysis of copper lms during sintering of (a) copper nanoparticle ink and (b) copper microparticle ink
(reprinted with permission from ref. 76).
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SEM micrograph representing the morphology of copper ink sintered by laser with power and scan rate as (a) 69 W cm2, 1 mm s1, (b)
148 W cm2, 1 mm s1 and (c) 190 W cm2, 2 mm s1 respectively (reprinted with permission from ref. 77).
Fig. 80
Fig. 83
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(a) Schematic representation of mechanical fatigue tester, (b) image of sintered ink for the fatigue test and (c) calculation of bending
radius of the patterned conductive ink (reprinted with permission from ref. 78).
Fig. 84
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precursors. A Cu2ZnSnS4 nano-crystal based ink was synthesized by Agrawal et al.84 for application in solar cells.
Transparent electrodes have been fabricated using copper
nanowires as an alternative for photovoltaics, OLEDs (organic
light emitting diodes), touch screens, etc. Traditional transparent electrodes are replaced by these copper nanowire-coated
transparent substrates. The optical responses (absorbance,
transmittance and reectance) of these fabricated transparent
electrodes were observed to be better than the conventional ITO
and FTO.
Fig. 87
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Schematic comparing (a) inkjet and (b) spray coating (reprinted with permission from ref. 85).
Fig. 92
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Fig. 94
ref. 85).
Polymer coating
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Nano copper (b) LLDPE and (c) CuO (reprinted with permission from
ref. 103).
LLDPE (maleic anhydride graed linear low-density polyethylene) and an antioxidant (n-octadecyl-3-(4-hydroxy-3,5-ditert-butyl-phenyl)-propionate) were used, with which a ne
powder of CuO was used as an initial precursor. The characterization results show the purity of the obtained copper nanoparticles.
The XRD patterns of the prepared nano-Cu, LLDPE and CL15 (nano-Cu with 5% mass) are illustrated in Fig. 96. It can be
clearly observed that the peaks in Fig. 96 correspond to pure Cu
and no impurity or metal oxide is detected by XRD, indicating a
pure nano-copper product. The EDS analysis in Fig. 97 shows
Fig. 98
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Carbon/graphene encapsulation
SEM images of (a) initial material CuO, (b) prepared nano-Cu and (c) CL-15 (reprinted with permission from ref. 103).
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Fig. 99 Schematic of dry coating equipment: (a) cylindrical chamber with three grooves where copper nanoparticles were placed, (b) source
bottle in which to place the organic solvent (octanethiol in this case) and (c) joint connecting the small chamber to the main chamber (reprinted
with permission from ref. 106).
Fig. 101 TEM images of copper nanoparticles dry-coated with octanethiol (reprinted with permission from ref. 106).
Fig. 102 (a) XRD of commercial copper and (b) XRD of carbonencapsulated copper (reprinted with permission from ref. 104).
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Fig. 106 TEM images after the synthesis of nanoparticles: (a) TEM of
nanoparticles obtained at 500 C, (b) corresponding HR-TEM image of
a single particle, (c) TEM image of particles at 700 C and (d) HR-TEM
image showing the layer of carbon at the outer shell (reprinted with
permission from ref. 107).
Fig. 104
Fig. 105 XRD and Raman analysis: (a) comparison of conventional copper peaks and graphene/copper peaks and (b) Raman spectra of the
synthesized particles (reprinted with permission from ref. 107).
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7.4
Silica coating
Fig. 108
Schematic representation of mechanism of formation of metallic coreshells of CuAg (reprinted with permission from ref. 105).
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ref. 110).
8. Applications
Conductive copper inks have a wide range of applications in the
eld of electronics, automation communications, energy harvesting, MEMS/NEMS devices, display devices, computer
peripherals, biological sensors, etc. (Fig. 111113)
Flexible circuits for membrane touch switches are one of
the best applications of conductive inks due to the cost of
manufacture when compared to the conventional methods in
fabricating them.
Flexible keyboards for desktop and notebook PCs can be
fabricated using conductive inks, where the interconnections
present inside the keyboard can be replaced via inkjet printing
of conductive inks.
Conductive copper inks can be used in the fabrication of
automotive sensors which are used in automobiles for better
performance, safety and control. Automotive sensors include air
bag sensors, engine failure sensors, fuel sensors, parking
sensors, brake sensors, etc.111,112 MEMS devices are used in the
fabrication of these automotive sensors where conductive ink
can be applied.
Biosensors, one of the widely known recent technologies in
the eld of science, can be fabricated using conductive inks.
Fig. 111 Relative market size for printed and exible sensors in 2024
(reprinted from ref. 113).
Fig. 113 Market value share for conductive inks in all applications
20142023 (reprinted from ref. 110).
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Fig. 116 Electronic contact lens for ophthalmologic implants (reprinted from ref. 124).
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Table 2
Group name
University/Institute
Research areas
Reference
Lewis Lab
Harvard University
125
University of Illinois
Stanford University
University of Toronto
Electronics Laboratory-Wearable
Computing
126
127
128
129
130
131
132
133
134
135
136
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12.
Conclusion
In this review, we have tried to bring into light all the possible
methods for the synthesis of copper nanoparticles and
conductive inks. However, only a few synthesis techniques have
been successfully applied in conductive inks. Initially, conductive inks were prepared using copper nanoparticles that were
synthesized via chemical reduction. Among the above-discussed
chemical reduction methods, all the synthesis techniques discussed in this review are unique in synthesizing copper
Acknowledgements
Authors are thankful to CSIR-TAPSUN for nancial support. We
also gratefully acknowledge DST-UK (APEX) for their support.
Authors show their gratitude to all the researchers who
contributed to the work cited in this article.
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