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RSC Advances

REVIEW

Cite this: RSC Adv., 2015, 5, 63985

Copper conductive inks: synthesis and utilization in


exible electronics
Venkata Abhinav K,a Venkata Krishna Rao R,a P. S. Karthika and Surya Prakash Singh*ab
Conductive inks are a recent advance in electronics and have promising future applications in exible
electronics and smart applications. In this review we tried to focus on a particular conductive ink that is
based on copper nanoparticles. Although extensive research is being done all over the world, a few
complications are yet to be perfectly solved. We tried to focus on some of the complications involved in
their synthesis and their various applications in the dierent elds of science. Conductive inks have
promising applications in the present trends of science and technology. The main intention behind this
review is to list some of the best methods to synthesize copper nanoparticles according to the method
of synthesizing them. We chose copper nanoparticle synthesis and the preparation of conductive inks

Received 4th May 2015


Accepted 22nd June 2015

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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the obtained conductive patterns are also included.

1. Introduction
Nanotechnology is a rapidly developing advance and its products are extremely useful in all elds, in view of their small size

Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical


Technology, Uppal Road, Tarnaka, Hyderabad-500007, India

Network Institute of Solar Energy (CSIR-NISE), Academy of Scientic and Innovative


Research (AcSIR), New Delhi, India. E-mail: spsingh@iict.res.in

Dr Surya Prakash Singh is a


Scientist at the CSIR-Indian
Institute of Chemical Technology, Hyderabad. He studied
chemistry at the University of
Allahabad, India, and obtained
his D.Phil. degree in 2005. Aer
working at the Nagoya Institute
of Technology, Japan, as a postdoctoral fellow, he joined Osaka
University, as an Assistant
Professor. He worked as a
researcher at the Photovoltaic
Materials Unit, National Institute for Materials Science (NIMS),
Tsukuba, Japan. He has been involved in the design and synthesis
of materials for organic solar cells and exible devices. He has
published over 100 papers and reviews in peer-reviewed journals.

This journal is The Royal Society of Chemistry 2015

(109 m) and substantial surface range. Nanoparticles oer a


larger surface-to-volume ratio when compared to macro- and
micro-materials. The extraordinary properties of nanoparticles
are because of a solid exchange between versatile, geometric,
and electronic parameters. The consequence of these features
can be tuned by physical and substance properties contrasting
with those of the mass material.1 The examination of nanoparticles has attracted wide interest in the most recent decades
on account of their strange and size-dependent optical,

Venkata Abhinav K is a research


student at the CSIR-Indian
Institute of Chemical Technology, Hyderabad, India, in the
group of Dr Surya Prakash
Singh. He completed his Bachelors degree in Electronics and
Communication engineering at
Jawaharlal Nehru Technological
University, Hyderabad, India.
His research interests are
focussed
on
synthesizing
conductive nanomaterials using
various techniques and applying them in the eld of printed electronics. He is also interested in self assembly of fullerenes and
fabrication of solar cells using cost eective materials.

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attractive, electronic, and compound properties. To completely


use these properties, the size and shape must be eectively
controlled. This technology has gained a lot of importance in
recent years due to its applications in multi-disciplinary elds
(biology, chemistry, electronics, pharmacy, cosmetics, energy,
etc.). This is one of the promising technologies for the future
due to its advantages over the present technologies and their
applications.2
The incorporation of nanotechnology in the eld of electronics was initiated more than a decade ago. Even though vast
research is being conducted in this eld, much more has to be
done to implement them in real-time applications. We tried to
focus on one of the sub-elds of electronics i.e., exible electronics. Flexible electronics is a contemporary eld which has
applications in energy harvesting, touch screens, solar panels,
microcontrollers, paper electronics, PCBs (printed circuit
boards), etc. The top three metals in terms of conductive
applications are silver, copper and gold. Silver is a widely known
metal as an ornament due to its lustrous character. Its added
advantages are it being the most conductive element (6.30  107
Siemens meter1 at 20  C), its thermal conductivity that can
withstand extreme temperature conditions, very good reectance, anti-bacterial nature, corrosion-free capacity, etc. Apart
from all the advantages silver is considered to be one of the
most expensive metals and it is very much less abundant in the
earths crust (68th place with 7.9  106%). The second element
with high conductance aer silver is copper.
Copper is a reddish element with a bright metallic lustre. As
with other metals, copper is also malleable and ductile and it is
the 26th most abundant element in the earths crust with
0.0068% availability.3 The name copper was derived from aes
cyprium a Latin word which means from the land of Cyprus4
and it was later changed to cuprum and to copper in English.
The electron conguration of copper is [Ar].3d10.4s1; it has one
free electron in its outermost shell which contributes to its
conduction. The atomic number of copper is 29 with atomic
weight 63.546. The melting and boiling points are 1084.62  C

and 2562  C, respectively. The structure of copper is FCC with


possible crystal morphologies of cubic {100}, octahedral {111},
dodecahedral {110}, tetrahexahedral {530} and their
combinations.
In this review we have tried to focus on the synthesis of
copper nanoparticles and the preparation of conductive inks
with the synthesized copper particles (Scheme 1). Copper
nanoparticles have shown promising applications in several
technological elds as thermal dissipation agents, antimicrobial and anti-fungal agents, lubricants, metal injection
moulding, catalysts, exible electronics, transparent conductors, etc. Copper nanoparticles5 have been obtained basically
using three dierent approaches, physical, chemical and biological; however, biological synthesis was referred to as a subdivision of chemical processes. The physical approaches
includes thermal evaporation, laser ablation, spray pyrolysis,
ball milling, etc., whereas the chemical synthesis processes
include electrochemical, chemical reduction, photochemical,
sono-chemical, polyol, etc.
Copper lms are of high interest for their use as interconnecting materials in multilevel integrated circuits, because
of their high conductivity (59.88  106) and excellent electronmigration resistance.6 Various methods for the preparation of
Cu lms have been reported and the most extensively investigated methodology has been MOCVD (metalorganic chemical
vapor deposition) due to its advantages of uniform step
coverage and selectivity. However, solution deposition also has
potential and, in particular, electro-deposition has proved
capable of eective integration in standard complementary
metal oxide semiconductor (CMOS) processes as well as
production of nano-structured layers.
Copper has very few disadvantages when compared to silver,
such as low conductivity and high oxidation tendency when
exposed to the atmosphere.6 Copper has advantages of low cost
and high thermal and electrical conductivity (aer silver).
Therefore, it is best to select copper over silver. The synthesis of
pure (oxide free) copper nanoparticles requires very clean and

Venkata Krishna Rao R is a


research student at the CSIRIndian Institute of Chemical
Technology, Hyderabad, India,
in the group of Dr Surya Prakash
Singh. He completed his Bachelors degree in Electrical and
Electronics
Engineering
at
Jawaharlal Nehru Technological
University, Hyderabad, India.
His research interests are
focussed on synthesizing various
conductive nanomaterials using
dierent techniques and applying them in the eld of exible
electronics. He is also interested in self assembly of fullerenes,
conductive inks and fabrication of photovoltaics using cost eective materials.

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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Review

Scheme 1

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Flow chart of synthesis of Cu nanoparticles and its application as ink.

non-corroding conditions because copper posseses an inherent


tendency to oxidize at room temperature very rapidly. The basic
requirement to synthesize copper nanoparticles is that the
nanoparticle growth part should be carried out in inert atmosphere or in the presence of nitrogen. Some methods to reduce
the eect of oxidation have also been reported and discussed in
this review. These techniques can be used to synthesize
conductive copper inks, which are our main interest. To prepare
high quality conductive inks, certain procedures and methods
have been followed and are explained in this review. Some
chemical methods to synthesize copper nanoparticles are

This journal is The Royal Society of Chemistry 2015

explained,7 from which some are further processed to make


conductive inks that can be used as a subcomponent of exible
electronics. They are:
 Chemical reduction;
 Polyol synthesis;
 Electrochemical synthesis;
 Photochemical synthesis;
 Microwave-assisted synthesis;
 Biological and green synthesis;
 Sonochemical synthesis;
 Hydrothermal and solvo-thermal synthesis.

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2. Techniques in synthesizing copper


nanoparticles
As mentioned above, copper nanoparticles can be synthesized
using many techniques. Chemical reduction is the most widely
used technique for the preparation of copper nanoparticles. The
polyol method, microwave synthesis, photochemical synthesis,
and electrochemical chemical syntheses are very rarely used.
Some of the best methods for synthesizing copper nanoparticles
using the above mentioned techniques are explained in detail
below.
UV-visible absorption spectra of copper nanoparticles with
water as a function of PVP concentration, acting as a stabilizing agent
(reprinted with permission from ref. 8).

Fig. 1

2.1. Chemical reduction


Reduction can be termed as a reaction that involves the gain of
electrons. For example, when iron forms rust, oxygen gets
reduced whereas iron gets oxidized. Using the same concept,
copper nanoparticles can also be synthesized by chemical
reduction, where the copper salt gets reduced to copper and the
corresponding reducing agent gets oxidized. Reduction is one
of the most prominent and widely used processes for synthesizing metallic nanoparticles. Many methods have been reported for synthesizing copper nanoparticles via chemical
reduction in the vicinity of dierent capping agents. However,
the use of PVP as a stabilizing agent has been the most reported,
although the combination of PVP with CTAB was also reported.
Along with PVP, dierent stabilizing agents like oleic acid,
carboxylic acids (glycolic acid, lactic acid, acetic acid, etc.),
PAAm, PEG, etc. were also used. Some of the best methods to
synthesize copper nanoparticles using chemical reduction are
explained in detail.
2.1.1 Using PVP. Huang et al.8 reported a method for the
preparation of copper nanoparticles synthesized by the reduction of 0.01 M copper(II) acetate dispersed in ethanol. The
reaction mixture was made by adding the copper acetate
ethanol dispersion to 5 ml 2-ethoxyethanol in the vicinity of
poly(n-vinylpyrrolidone) (PVP) (PVP was used in dierent
concentrations i.e., 0.2, 0.5, 1.0 wt%). In response, Cu2+ ions in
the mixture were reduced to copper metal by the inhibition of a
surplus of hydrazine-monohydrate under reuxing conditions.
The total synthesis process was carried out in a nitrogen environment to prevent the particles from oxidizing. The same
process was repeated using water as a replacement for 2ethoxyethanol. The same method was used for the preparation
of the nanoparticles through this particular arrangement and
allowed the eective combination of polymer-coated copper
nanoparticles. By the use of dierent amounts of PVP, copper
nanoparticles of dierent sizes were obtained.
The characterization of the particles was carried out by the
utilization of transmission electron microscopy (TEM) as well as
UV-visible spectroscopy. The non-linear optical properties of the
copper nanoparticles were determined utilizing the Z-scan technique. UV-vis characterization was carried out for measuring the
absorbance of the obtained copper nanoparticle colloid.
Depending on the concentration of stabilizing agents, the absorbance varied, exhibiting a surface plasmon resonance (SPR) in the
range of 570 nm to 582 nm, as shown in Fig. 1 and 2.

63988 | RSC Adv., 2015, 5, 6398564030

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.

Z-Scan plot representing the plot of transmittance vs. sample


position to determine the non-linear optical characteristics of the
obtained copper nanoparticles (reprinted with permission from ref. 8).

Fig. 3

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Review

Li et al.11 has reported a method to synthesize copper


nanoparticles. The precursors used are copper nitrate trihydrate
(Cu(NO3)2$3H2O), poly(vinylpyrrolidone) (PVP K-30) and
hydrazine hydrate (N2H4). Copper nitrate was reduced to
metallic copper nanoparticles with the hydrazine hydrate in the
presence of PVP, which acts as a stabilizing as well as capping
agent.
The obtained nanoparticles were characterized using SEM,
a UV-Visible spectrophotometer and XRD. The analyzed SEM
image is illustrated in Fig. 4. It can be clearly seen that the
obtained particles are uniform in size and shape with an
average size of 80 nm, as shown in Fig. 4. The UV-visible
spectra show that the copper particles have an absorption
band in the range of 550600 nm (ref. 12) with the highest
absorption rate at a wavelength of 596.5 nm. The XRD peaks
represent diraction at 43.6, 50.7 and 74.45, representing the
(111), (200) and (220) planes of the FCC crystal structure of
pure copper without any impurities. The reason for this antioxidizing nature being due to the presence of PVP as a
capping agent.
Takuya et al.13 synthesized copper nanoparticles using a
liquid phase reduction method. The source of copper is copper
acetate. Copper acetate is dissolved in distilled water and
sodium borohydride (0.1 mol dm3) is added to the copper
acetate solution. Here, sodium borohydride acts as a reducing
agent and polyvinyl pyrrolidone (PVP (Mw  10 000)) in varying
quantities (0.5, 0.1 and 2.0 g) was used as a stabilizing agent.
The mixed solution was reuxed at 20  C for 1 h. Aer one hour,
a black colloidal dispersion of copper nanoparticles was
obtained. The experiment was carried out in dierent atmospheres (nitrogen, oxygen and atmospheric air).
Characterization was carried out using TEM and HRTEM,
and simultaneously a SAED pattern was recorded for the
obtained copper nanoparticles. The TEM images of the copper
nanoparticles demonstrate the variation of morphology of the
nanoparticles depending upon the ambient conditions. The
particles obtained under a N2 environment are spherical and
elliptical in shape, as illustrated in Fig. 5a, with a size range of
530 nm. Nanorods are formed when the synthesis process is

Fig. 4

SEM image of copper particles (reprinted with permission from

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).

carried out in atmospheric air, which are illustrated in Fig. 5b.


The average aspect ratio of length to breadth was determined to
be 20 : 2. The average size was 5 nm and these nanorods line up
in several straight lines which leads to long chains. When the
synthesis of copper nanoparticles is carried out in an oxygen
environment the particle size was comparatively smaller (3 nm),
as shown in Fig. 5c.
The particle morphology is also dependent on the quantity of
PVP used in the synthesis process. When 0.1 g of PVP is used,
the nanoparticles formed are in the shape of a cube, as shown in
Fig. 6a. If 2.0 g of PVP is used, spherical nanoparticles are
formed under atmospheric air conditions, as shown in Fig. 6b.
When a moderate amount (0.5 g) of PVP is used as a capping
agent, a combination of rods and spheres are formed, as shown
in Fig. 6c.
Sampath et al. synthesized jasmine bud-shaped copper
nanoparticles14 by selecting copper(II) sulphate pentahydrate,
isonicotinic acid hydrazide, L-ascorbic acid, sodium hydroxide
(NaOH) and poly-vinylpyrrolidone as precursors. Copper
sulphate was dissolved in Milli-Q water and was added to the
solution containing 1% PVP. The solution of NaOH in deionized water was added to adjust the pH (greater than 7) of
the copper salt solution and stirred for 1 h. Ascorbic acid was
dissolved in de-ionized water and added to the copper solution
and stirred for 1 h, maintaining the solution at room temperature. Aer 1 h the temperature is raised to 70  C and the

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Fig. 8 AFM image of copper nanobuds (reprinted with permission


from ref. 14).

TEM images with varying concentration of PVP in air: (a) 0.1 g,


(b) 2.0 g and (c) 0.5 g (reprinted with permission from ref. 13).

Fig. 6

solution stirred for 10 min. The obtained ascorbic acid solution


was added to the reaction mixture dropwise; the colour of the
reaction mixture turns to yellow, indicating the formation of
copper nanoseeds. 0.001 M isoniazid was added gradually to the
reaction mixture; the colour of the reaction mixture changes
from yellow to reddish brown, which is an indication of the
formation of the copper nanobuds. The solution was then
centrifuged at 8000 rpm for 30 min and washed with ethanol
and dried under vacuum.

Fig. 7 TEM image of bud-shaped copper NPs (reprinted with

permission from ref. 14).

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The characterization of the obtained jasmine bud-shaped


copper nanoparticles was carried out using TEM, UV-visible
spectroscopy, XRD and AFM. The TEM image clearly show the
bud-shaped copper nanoparticles with a scale bar of 100 nm;
apparently the particle size is suspected to be less than 10 nm,
as shown in Fig. 7. The XRD peaks of the copper nanobuds
display diraction at 43.6, 64.5 and 77.7 corresponding to the
(111), (200) and (220) planes, respectively. The diraction at
64.5 represents an impurity, i.e., cupric oxide (Cu2O). The
obtained peaks have been matched with JCPDS no. 4-0836. It is
calculated that the average crystallite size is about 6.95 nm
(using the DebyeScherrer equation).
AFM was used to determine the height and structure of the
copper nanobuds and the obtained AFM image is in close
agreement with the obtained TEM results, as shown in Fig. 8.
The AFM measurement reports that the average size of the
nanobuds is 6.41 nm, which is approximately equal to the XRD
calculations. UV-visible spectroscopy shows that the surface
plasmon resonance phenomenon occurs at 573 nm and the
absorption band was located around 560570 nm, which is
reported to undergo a blue shi15 with decrease in size.
Yang et al. synthesized copper nanoparticles in an oblate
shape using a one-step large scale synthetic method with a yield
of 91.36%. The average size is calculated to be 80 nm and these
nanoparticles exhibited good anti-oxidation properties. In this
synthesis process,16 the precursors used were copper(II) oxide,
poly-vinyl pyrrolidone (PVP, K-30), hydrazine hydrate and
ethanol. Firstly, an appropriate amount of PVP was dissolved in
ethanol by stirring at a temperature of 40  C until a clear
solution was obtained. To this reaction mixture, copper chloride was added under vigorous stirring. Subsequently, hydrazine hydrate was injected into the reaction mixture and stirred
for 60 min. The change in colour of the solution from green to
henna colour indicates the growth of copper nanoparticles.
These particles were collected by centrifugation and washed
with ethanol and oleic acid. Aer washing, the copper nanoparticles were dried at room temperature.

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Fig. 10 XRD pattern recorded for copper nanoparticles stabilized with


(a) PVP, (b) CTAB and (c) a combination of PVP/CTAB (reprinted with
permission from ref. 17).

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).

The characterization of the dried copper nanoparticles was


carried out using TEM, HRTEM, UV-visible spectroscopy, XRD,
and FTIR. The TEM results show that the particles are in oblate
shape with an average size of 80 nm. A layer of PVP was also
detected and said to be the main cause of the size restriction of
the nanoparticles and the anti-oxidation property. The HRTEM
image displays the thickness of the PVP coated on the copper
nanoparticles, which is observed to be 8.72 nm as illustrated in
the Fig. 9. The obtained absorption peaks were dierent for the
two dierent concentrations of PVP (0.01 M and 0.015 M)
exhibiting surface plasmonic resonance at 603 nm and 596 nm,
respectively. The XRD peaks suggest that diraction occurs at
43.2 , 50.3 , 74.1 and 89.6 , which correspond to the (111),
(200), (220) and (311) crystal planes, respectively, which are
clearly FCC structured. Surprisingly, no diraction of oxides
was detected.
2.1.2 Using PVP & CTAB. Chen et al.17 synthesized air-stable
copper nanoparticles with an average diameter of 6.5 nm. The
precursors used for the preparation of the nanoparticles are
copper sulphate pentahydrate (CuSO4$5H2O), hydrazine
(N2H4$H2O), di-ethylene glycol (DEG), PVP and CTAB. The
copper source is copper nitrate, the reducing agent is hydrazine
and PVP and CTAB act as stabilizing agents18,19 with DEG as the
solvent. The reaction was carried out at a temperature of up to
80  C for about 30 minutes to 2 h. The same process was carried
out using a single capping agent, i.e., only PVP or only CTAB,
and the results were compared with the help of characterization
techniques. The synthesized nanoparticles were characterized
using XRD, TEM and FTIR for a clear understanding of the
obtained results.
The XRD analysis show that diraction peaks at 43.3 , 50.4
and 74.08 were obtained, as shown in Fig. 10, representing the

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(111), (200) and (220) diraction planes of the FCC structure


when PVP/CTAB are used, and a minor peak of copper oxide was
observed when using only PVP or CTAB.
TEM analysis was performed for all three dierent combinations. The importance of the PVP/CTAB combination can be
clearly seen from (Fig. 11a) the PVP-coated Cu NPs, (Fig. 11b)

Fig. 11 TEM micrographs of (a) PVP-Cu nano-particles, (b) CTAB-Cu


NPs and (c) PVP/CTAB (reprinted with permission from ref. 17).

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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).

the CTAB-coated Cu NPs and (Fig. 11c) the PVP/CTAB-coated Cu


NPs, reduced by hydrazine. It can be clearly observed from
Fig. 11 that the PVP/CTAB-coated copper NPs were uniform and
the same in size and shape, with a scale bar of 50 nm. The
average diameters of the PVP and CTAB coated Cu NPs are
reported to be equivalent to 14.03 nm and 12.35 nm, respectively, and the average diameter of the Cu NPs coated with a
combination of PVP and CTAB is nearly 6.5 nm. The main
reason behind this distinction in their diameters is due to their
relative rate of nucleation & growth and their tendency to
agglomerate. However, the growth of ner nanoparticles may be
due to the fact that PVP or CTAB as sole stabilizers have less
tendency to get adsorbed on the nuclei, therefore resulting in
rapid agglomeration. In the case of assorted capping agents, the

Review

adsorption onto the nuclei is better, which restricts the


agglomeration of the nanoparticles. FTIR spectroscopy was
performed to further examine the coordinative interactions
between the copper nanoparticles.
2.1.3 Using oleic acid. Jing et al.20 have reported a similar
method, using copper acetate as the source of Cu+ ions and
oleic acid as a stabilizing agent, with a reducing agent of
hydrazine hydrate and toluene as a solvent. The reaction
process was carried out in a nitrogen atmosphere for 30 min.
The temperature was maintained at 70  C for 3 h.
The size and shape of the copper particles were observed
using TEM. All the particles obtained were uniform in size and
shape, as shown in the Fig. 6. The XRD pattern was obtained
showing maximum diractions at 43 , 50 and 74 , which are
reported to be very close to the JCPDS le no. 4-0836. FTIR
analysis was carried out to understand the role of the organic
molecules used in their study. The TEM image is shown
in Fig. 12, showing the uniformity in size of the copper
nanoparticles.
Zhong et al.21 synthesized size-controlled and potentially
shape-controlled copper nanoparticles in organic solvents in
the vicinity of amine/acid capping agents. The synthesis
procedure involves reducing a copper(II) acetylacetonate
(Cu(acac)2)/octyl-ether solution in 1,2-hexadecanediol under
reuxing conditions at a temperature of 105  C with a constant
stirring rate for 10 min. The synthesis process is carried out in
an argon atmosphere. Oleic acid and oleyl amine were added to
the solution; aer the addition of both the capping agents, the
temperature of the solution was raised to higher temperature

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).

(150210  C). The solution is kept at this temperature for 30 min


then cooled down to room temperature. Finally, the reacted
solution was mixed with ethanol and the solution was kept
aside overnight for the precipitate to settle down. The precipitate is washed and dried with a stream of N2 gas. The obtained
nanoparticles were suspended in hexane and were kept ready
for analysis.
TEM, XRD, UV-Vis spectroscopy and TGA were performed on
the obtained copper nanoparticles. The TEM results explain the
change in the morphology with respect to the temperature of
the synthesis of the nanoparticles, as shown in Fig. 13. The XRD
peaks conrm the formation of copper nanoparticles exhibiting
diraction at 43.5, 50.6 and 74.3 at the [111], [200] and [220]
planes, respectively, which represent cubic symmetry without
any impurities. The UV-visible spectrum of the obtained nanoparticle solution was recorded, which displayed surface plasmon resonance at 600 nm. Thermogravimetric analysis was
used to test the relative composition of the organic stabilizing
agents, which results in the prediction that 39% of the mass is
due to the capping shell and the remaining 61% is copper.
2.1.4 Using carboxylic acids. Xiao et al.22 utilised a process
where copper acetate was used as the source of copper ions,

with carboxylic acids (lactic acid, acetic acid, glycolic acid,


glycine, alanine and citric acid) as stabilizing agents. Hydrazine
hydrate (50%) was added as a reducing agent for reducing the
Cu ions to metallic copper, which was observed as a function of
the change in the colour of the solution from blue to brown and
then to henna colour. The pH of the solution was monitored
using a mixture of ammonia and water. The temperature was
maintained at 40  C for 3 hours in an inert atmosphere.
The characterization was carried out using UV-Visible spectroscopy, TEM, FTIR and XRD. The UV-visible spectrum shows
that the absorption is in the range of 550600 nm. The typical
values of the absorption peaks for acetic acid, glycolic acid,
alanine, lactic acid and citric acid are observed at 616, 610, 601,
600 and 582 nm, respectively.
The TEM results show that the sizes of the copper nanoparticles vary with dierent concentrations of carboxylic acids.
The formation of nanoparticles also depends on the type of
carboxylic acid used for the particle preparation. For example,
in Fig. 14a it is clearly depicted that the sizes of the un-stabilized
copper nanoparticles are larger when compared to the stabilized nanoparticle dispersions (Fig. 15).

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).

This journal is The Royal Society of Chemistry 2015

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Fig. 16 XRD patterns of copper nanoparticles synthesized using


dierent carboxylic acids at a concentration of 14 mol l1: (a) acetic
acid, (b) glycolic acid, (c) glycine, (d) alanine, (e) lactic acid and (f) citric
acid (reprinted with permission from ref. 22).

The FTIR spectroscopy displays peaks at 16081561 and


13951375 cm1 which indicate stretching of carboxylates. The
amine peaks were obtained around 34003200 cm1. The strong

Review

absorption at 3400 cm1 is probably from the adsorbed water.


The peaks around 3400 cm1 showed the presence of the
hydroxyl groups of glycolic acid and lactic acid, respectively.
XRD patterns were recorded for the ethanol-washed copper
nanoparticles. The diraction is mainly observed at 43.2 , 50.3
and 74.1 for all the carboxylic acids, with miller indices (111),
(200) and (220), respectively (as shown in Fig. 16), which
conrms that the obtained structure is FCC, and a minor peak
for Cu2O was observed at 36.6 , representing the (111) index.
2.1.5 Using PEG. Thi et al.23 synthesized copper nanoparticles using copper(II) sulfate penta-hydrate (CuSO4$5H2O),
which acts as a copper source. The copper salt is dissolved in deionized water to obtain a blue-coloured solution. PEG 6000
(polyethylene glycol) was added to the copper salt solution.
Here, PEG acts as a stabilizing agent. The mixed solution is kept
under vigorous stirring until a clear solution is observed. The
reducing agents used are ascorbic acid (0.02 M) and sodium
borohydride (0.1 M). Firstly, a solution of ascorbic acid and
sodium hydroxide (NaOH) are mixed and added to the copper
salt solution, when a colour change (white to yellow) is
observed. Sodium borohydride solution is added and constant

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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Fig. 18 XRD peaks displaying copper nanoparticles stabilized in PAAm


or AAm with dierent molar ratios (reprinted with permission from ref.
24). Index for Fig. 18: PAAm or AAm/Cu molar ratios (R1 2.00, R2
97.0, R3 0.11 and R4 0.46).

stirring is maintained. Aer a certain amount of time, the


yellow solution changes to black/red, which indicates that the
reduction has started and copper nanoparticles are formed.
Characterization was carried out using TEM, FT-IR and UVvisible spectroscopy. The TEM images explain the importance
of PEG in the particle size; dierent ratios of PEG : copper (6 : 1,
7 : 1 and 9 : 1) were used and the particle size decreased with
the increase in quantity of PEG used, as illustrated in Fig. 17.
The UV-visible spectra of the same ratios of PEG and copper
nanoparticles exhibit plasmonic resonances at 562 nm and it is
also observed that as the percentage of stabilizing agent
increases, the absorbance decreases. The FT-IR spectra of PEG
and PEGcopper are compared, which explains the interaction
between the PEG and copper nanoparticles. However, two
absorption peaks appear with the copper nanoparticles at 1690
cm1 and 1760 cm1.
2.1.6 Using PAAm. The synthesis of copper nanoparticles
stabilized with nitrogen ligands was reported by Alvarez et al.24
In this method, nitrogen ligands like allylamine (AAm) and
poly-allylamine (PAAm) were used as stabilizers. Partially crosslinked polyallylamine (PAAMc) leads to the formation of nanoparticles with low yields and high stabilization, whereas the use
of linear PAAm leads to the formation of nanoparticles with
high yield and low-coating content. The synthesis process is
carried out by selecting copper sulphate pentahydrate (CuSO4$5H2O), distilled water, hydrazine, sodium hydroxide (NaOH)

RSC Advances

and PAAm as precursors. The source of copper is copper


sulphate, the reducing agent is hydrazine, PAAm is used for
stabilization of the copper nanoparticles and sodium hydroxide
(NaOH) is used to maintain the pH of the solution. Firstly,
copper sulphate is added to distilled water and stirred for 10
min at a temperature of 60  C. Subsequently, an appropriate
amount of PAAm solution (PAAm dissolved in distilled water)
was added drop-wise to the reaction mixture under vigorous
stirring. In time, sodium hydroxide (NaOH) solution dissolved
in distilled water was added drop-wise and made to react for 30
min followed by addition of hydrazine. This reaction mixture
was monitored at constant stirring at 60  C. The change in
colour (black) of the solution indicates the formation of copper
nanoparticles. The solution was then transferred to a centrifuge
tube and centrifuged at 15 000 rpm and washed with distilled
water and ethanol. The washed copper nanoparticles were dried
at 60  C for two hours. The synthesis of copper nanoparticles
was carried out by selecting dierent molar ratios of PAAm/Cu.
The characterization of the obtained copper nanoparticles
was accomplished using TEM, XRD and TGA. The XRD information shows the diraction that is identied for three
dierent samples containing three dierent molar ratios of
PAAm/Cu (2.00, 0.11 and 0.46). The diraction is observed at
43.4 , 50.5 and 74.0 for all three molar ratios, where the
sample with molar ratio R1 also displays trace peaks at 35.9
and 38.6 indicating that oxidation has started to form cuprous
oxide. The obtained peaks are comparable to the JCPDS number
04-0836 (ref. 25) shown at the bottom of Fig. 18. The average
crystallite size has been calculated using the DebyeScherrers
formula26,27 and was calculated to be 13 nm.
TEM micrographs for all the molar ratios of PAAm/Cu are
shown in Fig. 19. The TEM image of the copper nanoparticles
with PAAm/Cu at a molar ratio of 2.0 is shown in Fig. 19a. In this
case the yield was less and the average diameter was calculated
to be 3.9 nm. Fig. 19b shows the TEM image with the molar ratio
of AAm/Cu of 97.0, with an average particle diameter of 6.0 nm.
Fig. 19c shows the TEM micrograph of PAAm/Cu with a molar
ratio of 0.11; the yield with this particular molar ratio is high.
Fig. 19d shows the TEM image with a molar ratio of 0.46. In this
case, the average particle diameter was 55 nm.
2.2

Polyol synthesis

In polymer chemistry, polyols are compounds with multiple


hydroxyl functional groups. Glycerin, pentaerythritol, ethylene

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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glycol, polyesters, polyethylene glycol, polyurethanes and


sucrose are some examples of polyols.28 The polyol process is
described as a novel route for preparing ultra-ne nano-sized
metal particles such as those of copper, gold, palladium,
silver, nickel, cobalt, iron, their alloys, etc. The synthesis
procedure in the polyol method is carried out by suspending the
precursor material in the liquid polyol (nitrates, chlorides and
acetates are more soluble whereas oxides and hydroxides are
slightly soluble). The supernatant is stirred and heated to a
given temperature, which can reach the boiling point of the
polyol for less reducible metals and in the case of easily
reducible metals, the reaction can be carried out even at 0  C.
Copper nanoparticles stabilized in PVP were synthesized by
Moon et al.29 using the polyol method. The synthesized copper
nanoparticles were around 45 nm (approx.) in size and the
shape was observed to be spherical. The important parameters
for controlling the shape and size of the copper nanoparticles

Review

were the concentration of the reducing agent, reaction


temperature and rate of precursor injection. These parameters
are controlled to change the morphology of the copper nanoparticles. CuSO2, PVP, sodium phosphinate monohydrate and
DEG are the precursor materials for this synthesis. Firstly, the
desired amount of PVP was dissolved in DEG until a clear
solution was obtained, then dierent concentrations of sodium
phosphinate monohydrate were added to the reaction mixture
and heated. An aqueous solution of copper sulphate pentahydrate was injected into the hot reaction medium using a syringe
pump; the rate of injection was varied from 2 to 8 ml min1 and
the solution was stirred vigorously for 1 h. Aer 1 h, the reaction
mixture was cooled to room temperature and le until the
particles settled at the bottom. The precipitated nanoparticles
were later separated by centrifugation, washed and dried.
XRD, XPS, SEM and HR-TEM characterizations were performed. Phase composition and crystallite size were calculated

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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Fig. 22 SEM images of Cu NPs synthesized as a function of reaction


temperature: (a) 200  C, (b) 170  C and (c) 140  C (reprinted with
permission from ref. 29).

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

using XRD. The FCC structure of the nano-copper was


conrmed by the XRD data with corresponding planes at (111),
(200) and (220). No traces of characteristic impurities were
found through XRD. The surface of the obtained copper nanoparticles was analyzed through XPS, where a copper peak was
identied at 932.0 eV with very weak CuO peaks at 934.2 eV (ref.
30), as illustrated in Fig. 20a. The interaction that is achieved via
a coordination bond between Cu and PVP31 molecules is displayed in Fig. 20b and c. SEM micrographs were recorded when
varying all the reaction parameters. Fig. 21 displays the SEM
images of copper nanoparticles showing the size distribution of
the copper nanoparticles as a function of reducing agent
concentration (12.75 mmol, 17.53 mmol and 19.13 mmol). The
particle sizes were found to vary from 5472 nm depending on
the concentration of reducing agent used. The reason for the
variance in the size of particles can be explained as follows: if
the concentration of the reducing agent is high, there is an
enhancement in the reduction rate, which in turn favors a high
probability of nuclei generation, causing the particle size to
decrease. In this case, the formation of an impurity (Fig. 21c)

This journal is The Royal Society of Chemistry 2015

takes place due to the formation of an intermediate phase.


However, in the case of low reducing agent concentration, the
rate of reduction is slow and this favors the formation of larger
sized particles. A moderate reducing agent concentration helps
in the formation of small sized particles with less of the
impurity (Fig. 21b). Fig. 22 shows the SEM images of the copper
nanoparticles when varying the reaction temperature (200  C,
170  C and 140  C); the particle size range is 4553 nm. As the
temperature is high there is a chance of rapid generation of
copper particles resulting in multiple nucleations. In this
particular case, the particles formed are broader in diameter, as
shown in Fig. 22a. In a situation where the temperature of the
solution is low, the nucleation rate is slower and the nuclei
count is enough to reduce the concentration of copper atoms in
the limit of the critical supersaturation level, which further
results in monodispersed particles. Fig. 23 and 24 represent the
SEM images of the copper nanoparticles prepared by varying
rate of precursor injection (2 ml min1, 6 ml min1 and 8 ml
min1) at two dierent temperatures (200  C and 140  C)
resulting in particle sizes of 4763 nm. The HR-TEM image
suggests that the synthesized copper particles are mostly single
crystals with some of them possessing twin boundaries (amorphous), as illustrated in Fig. 25. The boundary thickness was

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Fig. 24 SEM images of Cu NPs synthesized at 140  C as a function of


precursor injection rate: (a) 2 ml min1, (b) 6 ml min1 and (c) 8 ml min
(reprinted with permission from ref. 29).
Fig. 23 SEM images of Cu NPs synthesized at 200  C as a function of
precursor injection rate: (a) 2 ml min1, (b) 6 ml min1 and (c) 8 ml min
(reprinted with permission from ref. 29).

measured to be 1.5 nm. The SAED pattern also corresponds to


the FCC structure without any traceable impurities.
Baldi et al.32 synthesized copper nanoparticles using a
microwave-assisted polyol method. PVP-stabilized copper
nanoparticles with a diameter range of 45 to 130 nm were
synthesized with very high yield and stability. The synthesis
procedure starts with dissolving the chelating agent (PVP) in
DEG, which was stirred until a clear solution was obtained and
heated using a microwave oven. Aer reaching a certain reaction temperature, two dierent DEG solutions containing
ascorbic acid and copper acetate were added to the PVP solution. A change in color from green to dark red is observed which
indicates that the nucleation process has started, resulting in
the formation of copper nanoparticles. The temperature of the
microwave oven was varied (60170  C) to study the eect of
heat treatment and it was found that the temperature was one of
the most inuencing factors in the morphology and growth of
the nanoparticles.
The obtained copper nano-suspensions were characterized
using UV-Vis spectroscopy, DLS, XRD and STEM. Fig. 26a shows
the dierent steps in the copper reduction during the synthesis
process. The copper acetate precursor solution was green and as
the reduction starts the color change is clearly observed, ending
in a dark red colour. Fig. 26b displays a comparison between

63998 | RSC Adv., 2015, 5, 6398564030

reduced copper and cuprous oxide particles, with absorption


peaks at 725 nm and 450 nm, respectively. The UV-vis spectra
were recorded as a comparison of the copper nanoparticles
synthesized at various temperatures with their reaction times is
shown in Fig. 27b and c. Fig. 27a displays the STEM image of the
copper colloidal solution with homogenous particle sizes, with
an average size of 46 nm and a standard deviation of 9 nm.
Fig. 27b illustrates the particle size distribution from the STEM

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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RSC Advances

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).

imaging technique. DLS analysis was performed to show the


size distribution of the copper colloidal solution, as illustrated
in Fig. 27c. The sizes of the particles that were synthesized at
dierent temperatures (60  C, 100  C, 140  C and 180  C) were
compared. The XRD results in diraction at 43.3 and 50.5
without any impurities, which is consistent with the FCC shape
of metallic copper (JCPDS card no. 4-0836). The colloid was
again characterized with XRD aer thirty days and no traces of
copper oxides were observed. The size, shape and structure of
the obtained copper nanocolloids are dependent on certain
parameters, namely inuence of reducing agent, synthesis
temperature, reagent addition temperature, rate of reagent
addition, etc.33,34 By varying the aforementioned parameters, the
morphology of the copper nanoparticles can be modied.
Copper nanoparticles were synthesized by Lee et al. using the
polyol method with an average diameter of 100 nm.35 A typical
experimental procedure includes the preparation of copper
nanoparticles stabilized in PVP in ethylene glycol solution using
the polyol method.29 Aer the synthesis process, PVP was
removed from the surface by heating it by means of RF plasma
arc discharge for 50 seconds. 1-Octanethiol was used to coat the

This journal is The Royal Society of Chemistry 2015

surface of the copper by heating it with separately designed


equipment. The heating was carried out in a vacuum under
ambient temperature and pressure conditions. Fig. 28
compares the copper nanoparticles before and aer coating
with 1-octaethiol.
Chokratan et al. synthesized36 ultra-ne copper powders with
a controlled size by the addition of sodium hydroxide. The
particle sizes are reported to vary depending upon the molar
ratios of the precursor solution. The synthesis procedure starts
with dissolving copper nitrate trihydrate in a solution of sodium
hydroxide and glycerol with dierent molar ratios (0 : 1 to 5 : 1),
as shown in Fig. 29, while maintaining a constant molar ratio of
copper nitrate : glycerol of 0.02 : 1. The reaction mixture was
reuxed at temperatures of 120  C to 160  C at a constant stirring rate. The stirring was stopped when the reduction process
was complete. The obtained copper nanoparticles were separated and washed with ethanol several times.
The obtained copper nanoparticles were characterized using
XRD, SEM and FESEM, where SEM and FESEM are employed for
particle size distribution and image analysis and XRD is
employed to nd out the crystallite size and structure. XRD

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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).

diraction patterns were recorded for the copper nanoparticles


synthesized with a Cu(NO3)2 : NaOH molar ratio of 2 : 1,
reuxed at 140  C and observed at dierent time periods (20, 30,
120 and 240 min) aer heating the solution. The SEM images of
the copper powders were obtained at various NaOH concentrations at a reuxing temperature of 140  C. It can be seen that
the sample prepared with low NaOH concentration at a reaction
time of 20 hours was non-uniformly agglomerated. The average
size of the obtained copper powders decreased with increasing
NaOH concentration, as shown in Fig. 30. The SEM images of

Fig. 28 TEM images of copper nanoparticles (a) after removing PVP

and (b) after coating with octanethiol (reprinted with permission from
ref. 35).

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copper powders synthesized at various reaction temperatures of


(a) 120  C, (b) 140  C and (c) 160  C, with a molar ratio of 3 : 1,
are shown in Fig. 31.
2.3

Photochemical synthesis

Photochemistry is a branch of chemistry dealing with chemical


synthesis upon irradiation with photons. It is the study of
chemical reactions that proceed with the absorption of sunlight
by atoms or molecules.37 One of the best examples of photochemical synthesis is photosynthesis. Degradation of plastics
and the formation of vitamin D with sunlight are also part of
photochemistry. Photochemistry is concerned with the
absorption, excitation and emission of photons by atoms,
atomic ions, molecules, molecular ions, etc. In photochemistry,
energy is absorbed or emitted in discrete quanta called photons
and the absorption of light leads38 to an electronic excitation,
where the whole process starts working. An example schematic
explaining the photochemical synthesis of articial oxygen by
RGO45 sheets is shown in Fig. 32, using the principles of
photochemistry. Copper nanoparticles have been synthesized
using many synthesis methods, some of which are briey
described below.
Copper metal nanoparticles have been synthesized by Kapoor
et al.39 by irradiation with 253.7 nm light, carried out using a low

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RSC Advances

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

pressure mercury arc lamp. A de-aerated aqueous solution of


copper sulphate, PVP (polyvinyl pyrrolidone) and benzophenone
was placed in a rectangular quartz cuvette. A 200 W low pressure
Hg lamp was used as the source of ultraviolet rays for irradiation
at 253.7 nm at ambient temperature. The cuvette was placed in
the reactor for photolysis. The incident number of photons was
determined using a tris(oxalato)ferrate(III) actinometer to be 5.0
 1015 cm2 s1. The solution was de-oxygenated by bubbling
nitrogen gas through it for 15 min and was excited with a fourth
harmonic output pulse of 35 ps duration with a laser ash
photolysis at a temperature of 20  1  C. The concentrations of
PVP and benzophenone inuence the particle size proportionately. A similar process was carried out by Giurida et al.44 by
using a bis(2,4-pentandionato)copper(II) complex illuminated in

the presence of monochromatic emissions at wavelengths of 254


nm or 300 nm, stabilized in PVP.
The synthesized solution was characterized using a UVVisible spectrophotometer. Optical absorption spectra were
recorded, which displayed an intense absorption band exhibiting SPR at 565 nm, which is in the prescribed range for copper
particles.40 TEM images of the sample composed of PVPstabilized copper nanoparticles were captured with a scale bar
of 20 nm, as illustrated in Fig. 33a. The size of the obtained
copper particles was found to be in the range of 15  4 nm. The
SAED pattern conrms that the obtained particles are polycrystalline in nature, as shown in Fig. 33b.
Nano-sized copper metallic particles and colloidal copper
nanoparticles were synthesized by Giurida et al.41 upon ultraviolet

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).

Spectral alterations in the visible region upon irradiation of


Cu(acac)2 solution in ethanol (reprinted with permission from ref. 39).

Fig. 34

An example schematic of photochemical synthesis (reprinted


with permission from ref. 45).

Fig. 32

irradiation of ethanol over bis(2,4-pentanedionate)copper(II)


[Cu(acac)2]. The copper colloid was obtained by irradiating the
solution of Cu(acac)2 in deoxygenated ethanol with 254 nm light in
the range of 106 to 105 Nhv min1.
A UV-vis spectrophotometer was used to monitor the specic
absorptions of the precursor solution at 242 and 294 nm. Also, a
new band was observed at 274 nm due to the chelation by 2,4pentanedione (Hacac). The absorption at 575 nm, as shown in
Fig. 34, was observed as a characteristic surface plasmon resonance band of copper in the colloidal state as a result of longer
irradiation. Aer aging of the colloidal copper, the X-ray
diractometer displayed diraction of the crystals at 43.3
and 50.4 in the (111) and (200) planes, respectively. SEM
analysis was performed for the investigation of size and

(a) TEM image of copper nanoparticles and (b) SAED pattern


(reprinted with permission from ref. 39).
Fig. 33

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morphology of the nanostructures formed by drying the


colloidal copper solution. Spherical particles with dierent size
distributions of 20 to 80 nm were conrmed by the SEM images,
as shown in Fig. 35.
Nie et al.42 developed a facile method for the preparation of
copper nanoparticles via ultraviolet irradiation of a solution

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).

containing a photo-initiator and a copper-amine compound.


Photoreduction of an ethanol solution of copper chloride using
a photoinitiator for the preparation of a copper nanoparticle
colloid was carried out by mixing CuCl2 in an ethanol solution
with photoinitiator-184 (1-hydroxycyclohexyl phenyl ketone).
The solution was irradiated with a xenon lamp from the transparent side of the cuvette for 40 minutes with a radiation
intensity of 45 mW cm2. The intensity of the irradiated light
was measured with the help of a ferric oxalate actinometer. The
total synthesis process was carried out in a vacuum glove box
because the preparation of the colloid is unstable in the presence of oxygen and hence it should be prepared in an oxygenfree environment and should also be preserved in a dark environment away from sunlight.
The photoreaction was monitored using a UV-vis spectrophotometer, and the product characterized using XRD for the
determination of the composition of the obtained copper
nanoparticles. The size and morphology was obtained using
TEM analysis. The diraction peaks at 43.55 and 50.66
correspond to the (111) and (200) planes, respectively, which
conrms that the precipitate is copper. Simultaneously, the
TEM images revealing the size and shape of the nanoparticles
showed that the size of the prepared particles synthesized using
the photo-reduction method was less than 100 nm, as shown in
Fig. 36. UV-vis spectra were recorded every 20 s to detect the
changes in absorption and the change in the colour of the

Fig. 38 TEM analysis of copper colloid synthesized by irradiating with


a 532 nm laser, irradiated with a power of: (a) 50 mJ pulse1 for 10 min,
(b) 50 mJ pulse1 for 30 min, (c) 115 mJ pulse1 for 30 min and (d) 300
mJ pulse1 for 30 min (reprinted with permission from ref. 43).

solution from blue to colorless, colorless to black and then


black to colorless (formation of precipitate). SPR was observed
in the 550600 nm range (approximately 575 nm) which is in
good agreement with the XRD and SEM results.
Colloidal copper was synthesized via laser irradiation of CuO
powder in the presence of 2-propanol by Yeh et al.43 The source
of laser irradiation was a Nd-YAG laser. A laser with a fundamental frequency of 1024 nm and second harmonic frequency
of 532 nm was used as a light source. CuO powder was dissolved
in 2-propanol and placed in a Pyrex vial to be irradiated by laser
beams of 1064 nm and 532 nm for the formation of a copper
nanoparticle colloid.
UV-vis spectra of the colloidal copper irradiated at wavelengths of 1064 nm and 532 nm were recorded. Peaks were
observed for the colloid prepared with irradiations of 1064 nm
and 532 nm due to the SPR phenomenon at 580 nm, which is
the characteristic peak of copper, with low absorbance. XRD
analysis was performed for the dried copper colloid, exhibiting
diraction at 43.2 , 50.3 and 73.3 corresponding to the
formation of metallic copper nanoparticles. TEM analysis was
performed for the copper colloid synthesized by irradiating at a
wavelength of 1064 nm; the shape of the particles was found to
be spherical with an average diameter of 55.9 nm, as shown in
Fig. 37. Fig. 38 shows copper nanoparticles synthesized by
irradiating at the wavelength of 532 nm. The average particle
size was found to be around 50 nm. From the TEM images
shown in Fig. 38, it can be clearly understood that the particle
size varies with the photon energy transmitted to sinter the
particles eectively.
2.4

Microwave-assisted synthesis

Fig. 37 TEM image of colloidal copper synthesized with irradiation at

1064 nm with a power of 100 mJ pulse1 for 5 min and 10 min,


respectively (reprinted with permission from ref. 43).

This journal is The Royal Society of Chemistry 2015

Microwave-assisted synthesis refers to the technique of


applying microwave radiation to promote a chemical reaction.

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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

(b) high magnication (reprinted with permission from ref. 49).

High frequency electric elds generated by microwaves have the


capability to generate controlled heat.46 The energy dissipated
by the microwaves has the ability to heat any material that
contains mobile electric charges, such as conducting ions or
polar molecules in a solvent. One of the advantages of
microwave-assisted synthesis is that the time taken for a reaction to reach completion is very much less when compared to
the other synthesis techniques.47 This is due to the fact that the
energy released is controlled and evenly distributed through the
chamber. Microwave-assisted synthesis of copper nanoparticles
has advantages of faster reaction times, rapid optimization,
higher yield and energy eciency.
A one-step chemical synthesis of copper nano-uids was
developed by Yin et al.48 The precursors used in this synthesis
process are copper sulphate pentahydrate (CuSO4$5H2O),
ethylene glycol, poly-vinylpyrrolidone (PVP) and sodium hypophosphite (NaH2PO2$H2O). Firstly, copper sulphate was dissolved in a solution of ethylene glycol and PVP and stirred for 30
min. An ethylene glycol solution of sodium hypophosphite was
added to the reaction mixture and stirred for 5 min. Aer 5 min,
the reaction mixture was put into a microwave oven and reacted
for 5 min under medium power. The copper nanoparticle
formation was conrmed by observing the change of the color
of the mixture from blue to dark red.

TEM images of copper nanoparticles synthesized using


CuSO4 at concentrations of (a) 0.2 M and (b) 0.5 M (reprinted with
permission from ref. 48).
Fig. 40

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The XRD pattern was recorded, exhibiting diraction as per


the JCPDS le no. 04-0838, corresponding to the planes at (111),
(200), (220) and (311). The diraction peaks can be indexed to
be a pure FCC structure. The TEM image reveals that spherical
copper nanoparticles, shown in Fig. 39 and 40, were obtained
with an average diameter ranging from 10 nm to 20 nm.
Surfactant-free synthesis of air-stable copper nanoparticles
was achieved by Shivashankar et al.49 Cu(acac)2 was dissolved in
benzyl alcohol in a round bottom ask and was exposed to
microwaves at 800 W for a time period of 3 minutes. The change
in the colour of the reaction mixture from blue to green and
further red indicates the formation of copper nanoparticles.
These copper nanoparticles were separated by centrifugation
and thoroughly washed with ethanol twice and diethyl ether
once. Aer washing, the particles were dried under vacuum. The
obtained copper nanoparticles were found to be free from
oxides even aer 12 months of exposure to ambient atmospheric conditions.
XRD spectra of fresh copper nanoparticles and copper
nanoparticles exposed to air for 12 months were compared and
found to be in good agreement with JCPDS no. 04-0836. The
average crystal size was determined to be 23 nm using the
DebyeScherrer equation. The low magnication FESEM image,
as shown in Fig. 41, was used to analyze the copper sample,
revealing that it consists of mono-disperse spherical particles
with an average diameter of 150 nm. The optical absorption of
the metal nanostructures was analyzed using UV-vis spectroscopy, which exhibits SPR at 580 nm with low absorbance. The
TEM images reveal the size, structure and morphology of the
metallic nanostructures, as shown in Fig. 42. The average size
was calculated to be close to 30 nm, which is similar to that
from the XRD analysis. The SAED pattern was also obtained,
which conrms that the obtained nanoparticles have a FCC
as shown in Fig. 42(c) and (f).
structure with d 2.08 A,
50
Zhu et al. synthesized functionalized copper nanoparticles
for application in glucose sensing. The copper nanoparticles
were functionalized with dimethylglycoxime using a microwave-

This journal is The Royal Society of Chemistry 2015

Review

RSC Advances

(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

assisted synthesis process. Copper acetate hydrate (CuAc2$H2O)


was reacted with dimethylglycoxime (DMG) dissolved in
ethylene glycol. The mixture was placed in a microwave reux
system under ambient conditions at a power of 365 W for 30
min. Aer 30 min, the reaction mixture was cooled to room
temperature and centrifuged to collect the precipitate. The
obtained precipitate was washed with distilled water, ethanol
and acetone and dried under vacuum.

The TEM image reveals the size, shape and morphology of


the obtained copper nanoparticles. DMG played a signicant
role in the dispersion of the copper nanoparticles, with
obtained diameters of 10 nm to 20 nm as shown in Fig. 43. A
comparison between the FTIR spectra of DMG and copper
functionalized with DMG was carried out. A noticeable dierence in the absorption band at 3419 cm1 was observed for the
DMG-stabilized copper nanoparticles. XRD peaks corresponding to the copper structure (CCID les no. 040836 Cubic),
exhibiting diraction at 43.3 and 50.4 in the planes of (111)
and (200), respectively, were found to be in close agreement
with the FCC structure of the copper nanoparticles.

2.5

TEM image of copper nanoparticles with an average diameter


in the range of 10 nm to 20 nm (reprinted with permission from ref.
50).

Fig. 43

This journal is The Royal Society of Chemistry 2015

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

Review

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).

SEM image obtained by electrodepositing lms with pH 13


(reprinted with permission from ref. 53).

Fig. 45

that are known to aect the morphology of the nanomaterial


are:
 Current density and pH of the electrolyte are kept constant
with variation of deposition time.
 Current density and deposition time are kept constant with
variation of the pH.
 Varying current density with constant pH and deposition
time.
Apart from the above mentioned parameters, voltage, power
and type of sacricial electrode also have an important role in
the synthesis of nanoparticles. Some methods to synthesize

Fig. 46 Schematic representation of bath used for electro-deposition


of Cu nanowires (reprinted with permission from ref. 54).

64006 | RSC Adv., 2015, 5, 6398564030

copper nanoparticles through the electrochemical method are


discussed in brief.
Copper nanoparticles were synthesized by Gupta et al.53 from
copper sulfate, sodium acetate, sodium hydroxide and sulfuric
acid using electrochemical synthesis. ITO was used as a working
electrode and Ag/AgCl as a reference electrode, while fullling
all the condition parameters. Spherical copper nanoparticles
and brous nanoparticles were obtained. The SEM images
reveal the shape and size of the obtained copper nanoparticles.
There is a variation in size and shape of the obtained nanostructures depending upon the parameters, such as pH, current
density, etc., as shown in Fig. 44 and 45. XRD analysis shows
that the copper nano-particles exhibited diraction in the
ranges of 25 to 40 and 60 to 70 corresponding to (111), (200)
and (220) planes, respectively.
Ahmad et al.54 synthesized template-based copper nanowires
using an electro-deposition technique. In this method, AAO
(anodized aluminium oxide) templates were used as one of the
electrodes (cathode) and a pure copper wire of 1 mm diameter
was used as the anode. The precursors used were copper chloride, dilute sulphuric acid and boric acid. The bath used
(Fig. 46) for the electro-deposition was controlled by a computer
to record the current density during the process. The copper
ions start migrating to the pores of the templates, are reduced to
copper metal and nanowires start growing.
FESEM was used to characterize the surface morphology of
the obtained copper nanowires. It can be clearly observed that

Fig. 47 FESEM image of Cu nanowires (reprinted with permission


from ref. 54).

This journal is The Royal Society of Chemistry 2015

Review

Fig. 48 EDX showing the presence of Al and O along with Cu

(reprinted with permission from ref. 54).

RSC Advances

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

Biological and green synthesis

The syntheses of nano-sized particles have gained utmost


interest during the past decade because of their peculiar properties, leading to their applications in multiple disciplines in
science and technology.56 Even though metallic nanoparticles
have a wide range of applications, their use is limited due to the
involvement of toxic chemicals in their synthesis process.57 To
overcome this limitation, metal nanoparticles can be synthesized
using non-toxic biosynthesis methods. Copper nanoparticles
have been synthesized using the biological method owing to their

Fig. 49 TEM image showing the presence of amorphous and crystalline structures (reprinted with permission from ref. 54).

the copper nanowires are aligned parallel to each other with a


high aspect ratio, as shown in Fig. 47. EDAX was used to characterize the composition of the synthesized copper nanowires.
In the EDX spectrum, aluminium and oxygen along with copper
are present, as shown in Fig. 48; the presence of aluminium and
oxygen may be due to the AAO templates. The TEM image
suggests that the diameter of the nanowires was around 15 nm,
with amorphous as well as crystalline structures, as shown in
Fig. 49.

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).

Fig. 52 SEM image of Cu nanowires showing uniformity in length and


diameter (reprinted with permission from ref. 55).

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

TEM images of Cu nanowires (reprinted with permission from

ref. 55).

applications in agricultural, industrial and technological elds.


Copper nanoparticles were synthesized in a single step by Thakare et al.,58 where starch was used as a stabilizing agent for
copper nanoparticles formed by the reduction of CuCl with
hydrazine hydrate. The average particle size obtained was in the

Other chemical synthesis methods

Apart from all the above mentioned synthesis techniques,


copper nanoparticles have also been synthesized using hydrothermal,61 solvo-thermal, thermal decomposition,62 pulsed wire
discharge,63 alcohol media reduction,64 dual plasma synthesis,65
and sono-chemical synthesis66 techniques, etc. Copper nanoparticles were synthesized using an electrochemical approach67
combined with graphene to enhance their conductivity and
improve the strength of the lms. Copper nanowires were used
to fabricate exible transparent electrodes through the electrochemical68 method, reduction69 and catalytic formation
process.70
Copper nanoparticles synthesized using the aforementioned
techniques have the tendency to possess a conductive property.
This property has been used in the synthesis of conductive inks.
Conductive inks can be synthesized via the addition of binding
agents to the synthesized copper nanoparticles. Some methods
to convert copper nanoparticles to conductive ink are explained
in detail herein.

3. Preparation of copper conductive


inks

Fig. 54 SAED pattern indicating Cu nanowires with a crystalline


structure (reprinted with permission from ref. 55).

64008 | RSC Adv., 2015, 5, 6398564030

Conductive inks were synthesized by Lee et al.,71 using 30%


weight of copper nanoparticles and 2-(2-butoxythoxy)ethanol. 2(2-Butoxythoxy)-ethanol was used as a dispersant for the copper
nanoparticles. The copper nanoparticles were dispersed by
thorough mixing in the dispersant for 15 min, followed by
microuidization. 0.4 mm syringes were used to completely
abolish agglomerated large particles. Aer ltration using a
micro-lter, the dispersion was used in an iTi industrial inkjet

This journal is The Royal Society of Chemistry 2015

Review

Fig. 56 Copper ink printed using an inkjet printer on polyimide


substrate (reprinted with permission from ref. 71).

printing system with a nozzle size of 38 mm. The temperature of


the substrate needs to be maintained at 85  C for the copper ink
to cure properly. Aer printing the copper ink on the substrate
surface, the substrate was sintered at 200  C for 1 h in a furnace
under nitrogen atmosphere. The printed pattern is shown in
Fig. 56.
The resistivity of the copper pattern printed on the polyimide
substrate was tested as a function of sintering time at 200  C.
The results shows that the resistivity was reduced up to 2.2
times when compared to bulk copper, as shown in Fig. 57.
Copper nanoparticle paste was synthesized by Yabuki et al.72
In the synthesis process, copper nanoparticles were dispersed
in a-terpineol (50% by weight) to make a nanoparticle paste.
The synthesized paste was coated on a glass substrate using the
doctor blade technique. It was later dried at 70  C for 15 min
and annealed under a ow of air, nitrogen gas or 5% hydrogen
argon mixed gas at 300  C for 1 h.
The morphologies of the copper patterns were analyzed
using SEM, as shown in Fig. 58 and 59, and the resistivities of

Fig. 57 Resistivity of copper pattern printed with the help of an inkjet


printer as a function of time at a sintering temperature of 200  C
(reprinted with permission from ref. 71).

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RSC Advances

Fig. 58 SEM images of copper patterns by annealing pattern in the


presence of (a) N2, (b) 5% H2Ar and (c) air & 5% H2Ar; (d) CuO lm
formed in the presence of air & 5% H2Ar (reprinted with permission
from ref. 72).

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

Fig. 59 Cross-sectional view of (a) copper at 300  C under air and 5%


H2Ar and (b) CuO pattern in 5% H2Ar (reprinted with permission
from ref. 72).

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Fig. 60 Resistivity of copper patterns at oxidation and reduction


temperatures (reprinted with permission from ref. 72).

Review

measurement, as shown in Fig. 63, and they were found to be


61.3 nU, 36.7 nU and 98.9 nU for copper lms printed 5, 10 and
20 times, respectively. A prolometer was used to determine the
thickness of the patterned electrodes, and the thickness
measurements were shown to be 1731, 3690 and 11954 nm for
5, 10 and 20 times printed patterns, respectively, as shown in
Fig. 64.
Pulsed wire evaporated copper nanoparticles were used in
synthesizing conductive ink for inkjet printing by Lee et al.63
Octanethiol-stabilized copper nanoparticles synthesized via
pulsed wire evaporation were dispersed in a mixed solvent of
DEG, isopropyl alcohol (IPA) and ethanol (DEG : IPA : ethanol
in the ratio of 6 : 2 : 2% by volume) and sonicated for 1 h. A
piezoelectric nozzle inkjet printer was used to print the
synthesized conductive ink onto a glass substrate. Aer printing
the copper patterns, they were sintered at 350  C for 4 h in the
presence of H2 or H2 + Ar (5.18 : 94.81 vol%) at a heating rate of
5  C min1.
The thickness of the copper pattern was measured using a
prolometer and the measurements are shown in Table 1. The
resistivity of the pattern was measured using a four-point probe
system and the measurements are shown in Table 1. SEM

Fig. 61 SEM of printed electrode (a) before sintering and (b) after
sintering (reprinted with permission from ref. 73).

a piezoelectric inkjet. A glass fabric/bismaleimide triazine (BT)


composite of 100 mm thickness was used as a substrate. The BT
substrate was heated up to 85  C when the patternization (5, 10
and 20 times printed) process was complete. Aer the patternization of the copper lm, it was thermally sintered at a
temperature of 200  C for more than an hour.
Morphological images of the printed copper pattern were
obtained using SEM. Images of the printed copper pattern
before and aer sintering were taken, as shown in Fig. 61 and
62. The resistivities of the lms were measured by four-probe

63 Resistivity measurements of printed copper patterns


compared to bulk copper (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

RSC Advances

Surface proles of copper patterns printed (a) 5 times, (b) 10 times and (c) 20 times (reprinted with permission from ref. 73).

Values obtained from electrical resistivity and thickness


measurements. N.A. not applicable

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

analysis was performed to analyze the surface of the patterned


substrate, as shown in Fig. 65.
Druel et al.75 synthesized copper ink via IPL (Intense Pulsed
Light) sintering. Tergitol NP-9, anhydrous Cu(NO3)2, ethylene
glycol, BaBH4 and NH4OH were used as the precursors for the

Fig. 65 SEM images of copper pattern sintered in (a) only hydrogen


and (b) a mixture of hydrogen and argon gases (reprinted with
permission from ref. 63).

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).

This journal is The Royal Society of Chemistry 2015

Fig. 67 XRD patterns of copper lms synthesized at pH 7, with EG; (b)


pH 11 with EG and (c) pH 11 without EG (reprinted with permission from
ref. 75).

preparation of the copper ink. Firstly, Tergitol was mixed with


an aqueous solution of Cu(NO3)2 in water. The pH of the reaction mixture was maintained from 7 to 11 by drop-wise addition
of NH4OH. Later, aqueous NaBH4 in water was added to the
reaction mixture. The same procedure was later repeated by
replacing water with ethylene glycol. The obtained solution with
ethylene glycol acts as the ink. The synthesized ink was ultrasonicated to break up the large agglomerates formed in the

Fig. 68 XRD patterns of copper lms prepared in presence of EG with


dierent concentrations of NaBH4 ((a)(d): 0.05 M, 0.1 M, 0.3 M, 0.6 M
respectively) (reprinted with permission from ref. 75).

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Images of conductive ink prepared at pH 11 in the presence of


EG, reduced using NaBH4 at concentrations of (a) and (c) 0.05 M (TEM),
(b) and (d) 0.6 M (HRTEM) (reprinted with permission from ref. 75).
Fig. 69

Sheet resistance vs. energy during the IPL sintering (reprinted


with permission from ref. 75).
Fig. 70

Review

synthesis process. Aer sonication, the ink was deposited on


glass substrates, which were preheated to 160  C. The copper
lms deposited on the glass substrate were sintered in an inert
nitrogen atmosphere with the help of light pulses. IPL sintering
was achieved by employing a xenon lamp to generate pulse of
incoherent light with a range of wavelengths varying from 190
nm to 1000 nm. The energy of the light pulses as well as the
energy densities was varied by varying the input voltages. To
sinter a conductive lm with a thickness greater than 5 mm,
more than one light pulse was required and hence 10 light
pulses were applied at each energy density. Copper lms were
also deposited on moisture-resistant polyester substrates which
possess a melting point of 150  C. The schematic of the preparation of inks with the IPL sintering process is shown in
Fig. 66.
XRD was employed to characterize the copper lms obtained
from IPL (intense pulsed laser) sintering. Films synthesized in
water as well as in ethylene glycol were analyzed, as shown in
Fig. 67 and 68. TEM and HRTEM images of the conductive ink
synthesized at pH 11 were recorded, as shown in Fig. 69.
Resistivity measurements are shown in Fig. 70, which were
carried out using a four-probe measuring instrument. Topographical images of the copper lms were recorded using SEM,

Fig. 72 (a) XRD pattern of IPL-sintered copper lm on exible PET


substrate, (b) SEM image of copper patterned exible substrate and (c)
digital photograph showing exible substrate with copper pattern on it
(reprinted with permission from ref. 75).

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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SEM images of (a) copper nanoparticle ink and (b) copper


microparticle ink after sintering (reprinted with permission from ref. 76).

Fig. 73

exhibiting a rough and porous structure, as shown in Fig. 71.


Applying IPL energy to the copper pattern caused the particles
to coalesce and thereby a change in morphology was observed,
as shown in Fig. 72.
Kim et al.76 synthesized a copper nano/micro-particle ink
which was used for fabrication of printed electronics by means
of ash light sintering. In their typical synthesis technique,
copper nano/micro-particles of 2050 nm diameter, with very
little oxide of a thickness of >2 nm, were chosen. PVP was
dispersed in DEG solution. To this reaction mixture, copper
nanoparticles were dispersed using a mechanical stirrer and
ultra-sonicator simultaneously for 3 h. The nal step for
preparing the ink is to ball mill the mixture for 12 h. The
synthesized nano/micro-particle ink was printed (at a thickness
of 20 mm) on a polyimide (PI) substrate and dried on a hot plate
at 100  C for 30 min. Flash light sintering is followed by drying,
where a xenon ash lamp was used for the sintering process.
The schematic representation of ash light sintering is shown
in Fig. 74, which compares the copper pattern before and aer
sintering.

Fig. 74

Fig. 75 XRD patterns of the sintered and unsintered copper nano/

microparticle inks (reprinted with permission from ref. 76).

The characterization of the copper lms was carried out


using XRD, SEM, four-probe methods and FT-IR. The resistivity
of the copper patterns was tested using the four-probe method
as shown in Fig. 76. In situ temperature and resistance tests
were carried out using a thermo-couple based circuit and
Wheatstone bridge during the sintering process. The XRD
patterns comparing the ink prepared using nanoparticles (sintered and unsintered) and microparticles (sintered and unsintered) are shown in Fig. 75.
As shown in Fig. 74, the nanoparticles were welded between
the microparticles, thereby acting as a contact between them.
The SEM image shown in Fig. 73 explains this more clearly.
Kang et al.77 synthesized a copper nano-ink by using copper
nanoparticles of diameter 100120 nm. These nanoparticles

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).

Fig. 77 Schematic diagram representing the system employed for


laser sintering (reprinted with permission from ref. 77).

were dispersed in a mixed solution of IPA (iso-propanol) and


PGME (propylene glycol methyl ether) to form a copper nanoink. The synthesized copper ink was spin-coated on a glass
substrate and dried at 50  C for 5 min. The thickness was
measured to be 1.3 mm. The schematic representation of the
system employed in laser sintering is shown in Fig. 77. A DPSS
(diode-pumped solid-state laser) with an average intensity of
190 W cm2 was utilized as the laser source for the sintering
process.

Specic resistance of copper lm with varying scan rates of 2


mm s1, 1 mm s1 and 0.6 mm s (reprinted with permission from ref.
77).
Fig. 78

64014 | RSC Adv., 2015, 5, 6398564030

XRD peaks of copper with scan rates of (a) 2 mm s1, (b) 1 mm


s and (c) 0.6 mm s1, sintered using a laser of power 190 W cm2 or
using hotplate with temperature of 300  C for (d) 120 s, (e) 20 s and (f)
10 s (reprinted with permission from ref. 77).
Fig. 79
1

The resistivity of the spin-coated conductive ink was


measured using a four-point probe, and is shown in Fig. 78. The
specic resistance of the lm tends to decrease when sintering
is carried out with an applied intensity of >100 W cm2. The
XRD spectrum of the spin coated copper lm prepared using
laser sintering with varying scan rate was compared to the
copper pattern prepared using thermal sintering as a function
of time, as shown in Fig. 79. The SEM micrographs are depicted
in Fig. 80, showing the surface morphologies of the copper
pattern sintered with increasing power. The SEM image clearly
shows that the grain size is increasing with the increase in laser
intensity.
Song et al.20 synthesized a conductive copper ink by mixing
copper nanoparticles in a solution of hydroxyl terminated
polybutadiene (HTPB) and toluene diisocyanate (TDI) in a threeneck bottle ask. To this reaction mixture, toluene was also
added as a viscosity lowering agent. The synthesized copper ink
was deposited on a glass substrate and annealed at 120  C for 2
hours.

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RSC Advances

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. 81 SEM micrograph of sintered ink composite prepared using (a)


90% Cu and (b) 60% Cu (reprinted with permission from ref. 20).

The characterization of the patternized ink was carried out


using SEM and XRD. SEM was employed for morphological
analysis. Morphological analysis enables the conductivity and
thin lm formation measurements. It is one of the most

Fig. 82 Conductive patterns of copper nano-ink fabricated using


gravure printing (reprinted with permission from ref. 11).

This journal is The Royal Society of Chemistry 2015

inuencing factors and is useful for determining the quality of


the conductive lm formation. Fig. 81a shows that connectivity
is achieved between the copper nanoparticles and the lm is
more prone to cracks because of the small grain sizes, whereas
Fig. 81b depicts the lm formation which is more promising for
enhancing the conductivity and is crack-free. XRD peaks are
obtained exhibiting diraction at 43 , 50 and 74 , which
correspond to the FCC structure of copper.
Luhai et al.11 synthesized a copper nanoparticle ink for
gravure printing. Copper nanoparticles were added to a
dispersion of ethylene glycol and glycerin additives. The
obtained copper colloid was re-dispersed by vigorous stirring
and ultra-sonication until it formed a paste. The obtained
copper paste was used for gravure printing of conductive
patterns. Gravure printed copper patterns are shown in Fig. 82.
The resistivity of the fabricated patterns was characterized
using a four-probe tester. By thermogravimetric analysis it was
found that the content of copper in the ink was 35.15% and that
of the stabilizing agent (PVP) was 1.29%, which will be removed
completely when the sintering is carried out, as shown in
Fig. 83.
Kim et al.78 synthesized a conductive ink by combining
copper nanoparticles and copper nanowires. The synthesized
conductive ink was employed to increase the reliability of exible electronics. The synthesis process was carried out by using
copper nanowires (150  50 nm diameter and 12 mm length)
and copper nanoparticles (2050 nm in diameter) as an additive
for attaining the conducting property. The additive mixture was

Thermo gravimetric analysis exhibiting residual mass of


copper and its mass change (reprinted with permission from ref. 11).

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

dispersed in a mixed solvent of PVP and DEG by mechanical


stirring and ultra-sonication for 2 h followed by ball milling for
24 h. The obtained material was further subjected to three-roll
milling three times for successful preparation of the conductive copper ink. The obtained conductive ink was coated on a PI
substrate using the doctor blade technique and dried at 100  C
for 30 min. The ratio of Cu nanowires and NPs was varied from
0% to 100% for the mechanical fatigue testing process. The
schematic representation of the fatigue tester is shown in
Fig. 84a.
A xenon ash lamp was employed for the sintering of the
fabricated copper patterns. Sintering of the copper patterns was
accomplished by irradiating the copper lm with an applied
energy of 7.5 J cm2 to 15 J cm2.
The characterization of the Cu NW/NP ink was accomplished
using SEM (morphological calculations), XRD (crystalline phase
calculations), the four probe-technique (resistivity calculation)
and a prolometer (measurement of the thickness).

of MOD inks over conventional nanoparticle inks is that the


metalorganic compound allows very low temperature sintering. The ink doesnt contain any particles and hence can be
used in printers. Another advantage of MOD ink is that an even
surface is formed aer the deposited ink is cured.74

4. Other types of copper based inks


Although the preparation of conductive inks was initially
accomplished by adding copper nanoparticles as additive
materials, self-reducing MOD (metalorganic decomposition)
inks are being synthesized in the present day. Piao et al.79 and
Magdassi et al.80 synthesized a self-reducible copper MOD ink
for use in exible and printed electronics. The main advantage

64016 | RSC Adv., 2015, 5, 6398564030

Fig. 85 PV device fabricated by using CuInSe2 (reprinted with


permission from ref. 81).

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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. 86 IV characteristics measured for the fabricated PV device


(reprinted with permission from ref. 81).

Schematic representation of the synthesis process used for


patternizing copper through ELD (reprinted with permission from ref.
82).

Fig. 87

Copper crystalline inks were prepared for application in


photovoltaic (PV) materials by Korgel et al.81 In their typical
synthesis process, chalcopyrite compounds, such as nano-sized
CuInS2, CuInSe2, and Cu(InxGa1x)Se2, were synthesized to
fabricate uniform and relatively thick nano-crystalline layers for
photovoltaic applications. A schematic representation for the
fabrication of PV devices using CuInSe2 ink is shown in Fig. 85.
Fig. 86 shows the IV characteristics for the fabricated PV
device.
The electro-less deposition (ELD) method was used by Wang
et al.82 for the inkjet printing of metallic patterns. ELD is an
auto-catalytic technique employed in depositing metals such as
copper, silver, gold, nickel, etc. Through ELD, the metallic
patterns can be deposited on substrates like paper, plastic,
alumina, etc. In a typical procedure, glossy photo-paper treated
with polyelectrolytes possessing quaternary ammonium was
used as a substrate. The schematic shown in Fig. 87 explains the
detailed process involved in the formation of copper patterns
using the ELD technique. The prepared ink was maintained at a
viscosity of 11 centipoises (cp), which is the optimum recommended range (1012 cp) for the viscosity of inkjet inks.89
Copper complex inks for application in photonic sintering
were synthesized by Sugahara et al.83 using copper formate
tetrahydrate, copper acetate and copper oleate as metallic

This journal is The Royal Society of Chemistry 2015

5. Techniques for patternizing


conductive inks
The synthesized copper conductive inks can be patternized by
using spin coating and spray pyrolysis. Some advanced printing
techniques have been used for the printing of conductive
patterns on exible as well as rigid substrates which can be
utilized in PV applications. Various types of printing techniques
have been employed in the successful printing of conductive
patterns.85,86 They are:
 Gravure printing90
 Screen printing93
 Inkjet printing95
 Flexographic printing98
 Spray coating100
 Knife coating
 Slot-die coating
 Double slot-die printing.93
Gravure printing has been used in the eld of electronics
since the 1980s. This technique was widely used and considered to be one of the most cost eective techniques employable
in everyday life. This type of printing is used in the fabrication
of solar cells, polymer eld eect transistors (PFETs) and
organic light emitting diodes (OLEDs).91,92 The schematic
illustration of gravure printing is shown in Fig. 88.
Screen printing is one of the most versatile printing techniques and was invented in the 20th century. This technique is
very simple to operate, is compatible with a large variety of
organic materials and has the ability to print under ambient
temperature and pressure conditions.94 The basic screen printer

Fig. 88 Schematic illustration of gravure printing (reprinted with


permission from ref. 86).

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Fig. 91 Schematic representation of exographic printing (reprinted


with permission from ref. 85).
Fig. 89 Schematic illustration of screen printing: (a) at-bed and (b)
rotary (reprinted with permission from ref. 86).

printing, in which a doctor blade is used to restrict excess ink.


The schematic illustration of exographic printing is shown in
Fig. 91.
Spray coating is similar to inkjet printing, as shown in
Fig. 92. In spray coating, ink is sprayed continuously on the
substrate. The spray is achieved by atomizing the ink, pressurized by air or gas (nitrogen gas), which helps in splitting the
liquid into droplets. A shadow mask is used while using spray
coating, which leads to low resolution of the printed pattern
and wastage of ink. Knife coating is one of the types of onedimensional coating. In knife coating, the ink is supplied in
front of the knife, which is placed near to the substrate, as
shown in Fig. 93. Knife coating has applications in fuel cells,
photovoltaic devices, etc.
In slot-die coating,98,99 a coating head is employed and is kept
very close to the printable substrate. A constant supply of ink is
used to print on the movable substrate. Using the slot-die
coating technique, high precision coating can be achieved.
Fig. 90 Schematic representation of inkjet printing (reprinted with

permission from ref. 86).

consists of only two parts, a squeegee and a mesh (screen), as


shown in Fig. 89. There are two types of screen printing, namely
at-bed screen printing and rotary screen printing. Screen
printing can be used to fabricate solar cells, fuel cells, organic
FETs, and organic thin lm transistors (OTFTs).
The key technology for printing in industrial usage is inkjet
printing. The advantages of ink-jet printing are accuracy, rapid
deposition rate, mask-less printing and non-contact mode, and
it can be used for the printing of a broad range of functional
materials.96 An ink-jet printer, as shown in Fig. 90, can be
operated in two modes, namely continuous mode and drop-ondemand mode.97 The exographic printing process has the
potential to achieve the required resolution and precision for
the printing of exible electronics and OLED lighting
substrates.99 Flexographic printing is similar to gravure

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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. 95 Schematic illustration of double slot-die coating (reprinted


with permission from ref. 85).

carbon nanotube inks, biological active layers, etc., can be


fabricated using the aforementioned coating processes.

6. Complications and challenges in


synthesizing conductive inks and their
remedies
Fig. 93 Schematic representation of knife coating (reprinted with

permission from ref. 85).

Double slot-die coating was used to print aqueous suspensions


of P3HT/PCBM and PEDOT/PSS solutions101 simultaneously in
the fabrication of organic photovoltaic cells, with a processing
speed of 1 m min1 (Fig. 94 and 95).
The aforementioned processes for copper conductive coatings have been also used for printing other types of metallic
coating, such as silver, gold, platinum, etc. Even non-metallic
coatings, such as carbon, graphene, polymer-based inks,

The main disadvantage in using copper nanoparticles in


conductive inks is that copper nanoparticles have the inherent
tendency to oxidize under atmospheric conditions, which is a
problem of great concern, as this oxidation has adverse eects,
such as decreasing the conductivity of the copper and
increasing the sintering temperature. Several methods have
been introduced by the researchers around the world to reduce
the eects of oxidation. However, the rate of oxidation depends
upon the surrounding atmosphere in which the nanoparticles
are synthesized and temperature and pressure have the most
inuence.

7. Methods to prevent oxidation of


copper particles
Magdassi et al.102 have discussed and determined some
methods for controlling oxidation on the surface of copper
nanoparticles. They are:
7.1 Polymer coating,
7.2 Carbon/graphene encapsulation,
7.3 Metallic coreshell preparation and
7.4 Silica coating.
All the above mentioned methods are successful in their
respective approaches, although some of the approaches have
shown enhancement in the conductive properties and some
failed to do so. Out of all the methods, the best method has to
be chosen for the preparation of oxide free nanoparticles
depending on their specic application and the cost of preparation for obtaining a good result with the product.
7.1

Fig. 94

Schematic of slot-die coating (reprinted with permission from

ref. 85).

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Polymer coating

Jiang et al.103 devised a method to prepare copper nanoparticles


with a polymer as the capping as well as stabilizing agent.

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Fig. 96 XRD pattern of copper nanoparticles stabilized with LLDPE. (a)

Nano copper (b) LLDPE and (c) CuO (reprinted with permission from
ref. 103).

Fig. 97 EDAX pattern of polymer-stabilized copper nanoparticles


(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

Review

that the product is composed of copper only. Similarly, the XRD


results indicate that no new phase has been found in the CuLLDPE nano-composite.
The SEM images of CuO, nano-Cu and CL-15 are compared
and are illustrated in Fig. 98. From Fig. 98, it is clear that the
morphology of nano-Cu is similar to that of CuO. It can be easily
observed that the shape of nano-Cu is nearly spherical. The SEM
image also shows that the particles obtained are pure copper
without any detectable impurity (oxides). The obtained size of
the copper particles is in close proximity to the required size
(i.e., 100 nm).
Lee et al.106 carried out dry coating of self-assembled monolayer (SAM) alkanethiol-stabilized copper nanoparticles. Unique
equipment was designed to dry coat SAM on copper nanoparticles, as shown in Fig. 99. The source of the equipment
contains a bottle of octanethiol. Ambient temperature and
pressures are maintained to coat the nanoparticles with evaporated octanethiol. Copper nanoparticles stabilized in PVP were
chosen for dry coating. PVP has to be removed from the surface
of the copper nanoparticles because SAM doesnt get coated on
the oxidized surface. For removal of the PVP, RF plasma treatment was used for 50 s. The TEM images, as shown in Fig. 100,
were recorded to conrm whether PVP had been removed. The
coating of copper nanoparticles with SAM was carried out by
heating the octanethiol liquid to 40  C under a vacuum of 4 
102 Torr. The evaporated octanethiol was coated on the surface
of the copper nanoparticles, which were placed inside the
cylinder and rotated at 25 rpm. To test the suitable coating
concentration of alkanethiol, copper nanoparticles were coated
by varying the number of coating cycles (6, 12 and 18). Aer
coating with SAM, TEM analysis was carried out, which
conrmed that there were no layers of oxide, as shown in
Fig. 101(b).
7.2

Carbon/graphene encapsulation

Carbon-encapsulated copper nanoparticles were synthesized to


prevent the copper from oxidizing. This method of synthesis
was carried out using the plasma arc discharge method by Hao
et al. A helium and methane environment is used in the
generation of the plasma arc and methane acts as a carbon
source.104 A vacuum of 0.1 MPa to 103 Pa is utilized, with a
discharge current of 80 A.
The size, morphology and surface characterization was
carried out using TEM, as shown in Fig. 103. XRD

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).

characterization, as shown in Fig. 102, was also carried out for


comparison, which clearly shows the presence of pure copper
(a) when compared with carbon-coated copper (b).
Later, it was found that the carbon coated on the copper is
amorphous, which fails in terms of conductivity and hence
cannot be used in the preparation of conductive inks.

Fig. 101 TEM images of copper nanoparticles dry-coated with octanethiol (reprinted with permission from ref. 106).

Therefore, an alternative for the conductive carbon material


should be used. In this case, a conductive carbon material like
graphene108 can be used.

Fig. 100 TEM image of PVP-coated copper nanoparticles (a) before


and (b) after plasma treatment (reprinted with permission from ref.
106).

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Fig. 102 (a) XRD of commercial copper and (b) XRD of carbonencapsulated copper (reprinted with permission from ref. 104).

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Fig. 103 TEM images depicting the amorphous carbon coated on


metallic nanoparticles (reprinted with permission from ref. 104).

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).

Schematic of vacuum-equipped furnace used for the


synthesis of graphene-encapsulated copper nanoparticles (reprinted
with permission from ref. 107).

Fig. 104

He et al.107 successfully prepared a conductive ink using


graphene-encapsulated copper to protect the copper from
oxidation. In their research they found that amorphous carboncoated copper nanoparticles have very poor conductivity. To
overcome this problem, graphene was used to encapsulate the
copper nanoparticles by coalescence. Graphene is a better
conductor, and hence the conductivity is not aected and there
is a chance of enhancing the conductivity due to the addition of
graphene.
The synthesis of graphene-encapsulated copper nanoparticles was carried out by placing Cu(acac)2 precursor in the
presence of hydrogen gas in a closed horizontal tube furnace, as
shown in Fig. 104, equipped with a vacuum pump. A temperature of 150600  C was maintained inside the furnace to test the
thermal stability and the ow rate of hydrogen gas was

maintained at 200 standard cubic centimeters per minute with


a pressure of 50 Pa.
The obtained nanoparticles were analyzed using X-ray
diraction, Raman spectroscopy and TEM. The thermal
stability of the nanoparticles was also examined using a thermogravimetric analyzer and the results were interesting.
The obtained XRD peaks clearly show that the graphene/
copper nanoparticles have the same peaks as conventional
commercial copper powder, as shown in Fig. 105a, which clearly
shows that copper is obtained with an average crystal size of 17
nm. The Raman absorption spectrum shows the formation of a
D-band at 1374 cm1 and G-band at 1588 cm1, as shown in
Fig. 105b, where the D-band exhibits the defects in the hexagonal sp2 carbon network and G-band corresponds to the
stretching motion of the sp2 carbon pairs in both the rings and
chains. In addition to all these rst order bands, second order
bands such as 2D and D + G bands are obtained, demonstrating
the formation of graphene-encapsulated copper particles.

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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Fig. 107 TEM images taken 60 days after synthesizing nanoparticles:


(a) low magnication TEM images taken showing the morphology and
structure of the particles and the SAED pattern, (b) HR-TEM image
showing the graphene layer outside the copper nanoparticles
(reprinted with permission from ref. 107).

TEM images are provided as a comparison, as shown in


Fig. 106.The images are taken at the time of synthesis and 60
days aer synthesis; in these 60 days the particles were exposed
to normal atmospheric conditions.
The comparison of the TEM and HR-TEM images shows that
there is no oxide layer formed, even aer 60 days. Fig. 107 shows
clearly that there are more layers of graphene, its thickness is
measured to be 0.21 nm and the orientation of the copper is
(111). This clearly shows that oxidation is prevented by deposition or encapsulation of graphene on the copper particles.
7.3

Fig. 109 Electron microscopy images of AgCu metallic coreshells:


(a) TEM of obtained coreshells, (b) HAADF-STEM image, (c) EFTEM
image depicting the CuAg particles and (d) HR-TEM showing the
dierence between both the particles by lattice fringes (reprinted with
permission from ref. 105).

7.4

Silica coating

A successful attempt has been made by Kobayashi et al.109 to


synthesize silica-coated copper nanoparticles. It is one of the

Metallic coreshell nanocomposite

Another method proposed by Cazayous et al. describes the


synthesis of CuAg core shell nanoparticles, where silver acts as
a protective coating against oxidation (corrosion). These
metallic coreshells are prepared using high vacuum thermal
evaporation equipment with an evaporation rate of 0.25 nm
min1 for copper and silver simultaneously.105 Structural characterization was carried out with the help of TEM, HAADFSTEM, EFTEM and HRTEM (Fig. 109).
Since there is no possibility for silver to be oxidized at
room temperature, these metallic coreshells do not oxidize
unless they react with any other acidic gases. There is a
possibility of enhancement of conductivity due to the presence of silver, which is more conductive than copper. The
preparation of CuAg coreshell metallic particles also
increases the cost of production, which is an important factor.
The mechanism of formation of coreshells of CuAg is given
in Fig. 108.

Fig. 108

Fig. 110 Comparison of XRD peaks of silica coated and uncoated


copper: (a) uncoated copper nanoparticles, (b) silica-coated copper
immediately after its preparation and (c) silica-coated copper after one
month (reprinted with permission from ref. 109).

Schematic representation of mechanism of formation of metallic coreshells of CuAg (reprinted with permission from ref. 105).

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inorganic attempts made to prevent oxidation of copper. The


XRD peaks illustrated in Fig. 110 are a comparison of silicacoated copper and un-coated copper. The XRD also shows
that the oxide of copper is formed when there is no inorganic
coating on the copper.
The XRD spectrum clearly shows the presence of copper
oxide (Cu2O) when not coated with silica (a); when coated with
silica (b) very little trace of oxide is found, as shown in
Fig. 110. Even aer one month it is observed that the silicacoated copper particles have not oxidized (Fig. 110c).
However, although silica is a very ecient protective agent, it
is an insulating material at room temperature and it possess a
high melting point, which restricts its use in the preparation
of conductive inks.

Review

Fig. 112 Conductive ink market by region up to 2018 (reprinted from

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).

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Fig. 113 Market value share for conductive inks in all applications
20142023 (reprinted from ref. 110).

Presently, gold ink114 is used in the fabrication of biosensors,


but in the near future, wearable biosensors may not be too far
away.

Fig. 114 Some recent developments in the eld of exible electronics.


From left to right and top to bottom: OLED TV, exible display for
mobile, printable photovoltaic cell, exible microuidic device, biological sensing tattoo for monitoring weight with the help of sweat
(reprinted from ref. 118122).

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 The Global Trend & Forecast to 2018 shows the Conductive


Ink Market by application (photovoltaics, membrane switches,
displays, bio-sensor, automotive) and type (silver ake & nanoparticle, copper nanoparticle, carbon/graphene, CNT, dielectric,
polymer).116

9. Recent developments in the eld


of exible electronics
Fig. 115 Patterning of bio-compatible self drawing sensors on human
body (reprinted with permission from ref. 117).

 Antennas for contact-free smart cards and RFID labels115


used for identication, asset management and security access
systems. A RFID inlay consists of an RF chip, antenna and
substrate in which the antenna can be fabricated using a
conductive ink.
 ITO-coated substrates are used as touch screens in
mobiles, tablets, laptops, etc. Transparent conductive electrodes
synthesized by using copper nano inks87,88 can be used as a
replacement for expensive ITO electrodes.
 Copper ink has applications in the printing of organic
photovoltaic devices (OPVs) which are fabricated using the
spray-mist coating method.100

Foldable and wearable electronics are the future of the present


electronics trend. The potential of these exible electronics is
unlimited. The need for exible electrodes is to enhance the
feasibility of managing bulk electronic devices. For example,
imagine a single sheet of plastic replacing all the books in your
backpack or a situation where every device is made to be nonbreakable. Its easy to use these exible devices because of
their advantages of light weight, foldable nature, low cost
involved in their production and controllability in their optical
and electronic properties,123 which make this technology a
stand out among others. This technological innovation can be
incorporated into display technologies, electronic papers,
biomedical implants, etc. Presently, some electronic devices
have been fabricated using this technology. OLED televisions,118
exible phone displays,119 printed solar cells,120 exible microuidic devices for protein screening (lab on a chip),121 foldable
biosensors for weight tracking,122 RFID tags,115 etc., are some

Fig. 116 Electronic contact lens for ophthalmologic implants (reprinted from ref. 124).

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examples of todays modern exible electronic technologies


(Fig. 114).

10. Future perspectives


In the current trend of the advancement of technology,
conductive inks play a vital role in achieving the goals of technological challenges. Synthesizing inexpensive conductive inks
is always a challenge for researchers. However, silver ink is
being used in many applications, although it is expensive and
has a negative impact on the device performance fabricated
with it. Conductive ink made of silver is being widely used for

Table 2

the fabrication of conductive as well as transparent electrodes


in photovoltaic applications.
Recent advancements made for synthesizing copper inks
have the potential to replace silver ink. The main advantages of
copper nanoparticle-based inks when compared to silver, graphene and CNT-based inks are its low cost of preparation and
abundancy compared to silver, and its excellent electron
migration resistance is also an added advantage. Sensing
applications are on the way to advancement, which may alter
and replace the conventional sensors that are being used today;
conductive inks can be utilized in the fabrication of sensors
using the latest technological changes. Replacement of

Active research groups working on exible devices

Group name

University/Institute

Research areas

Reference

Lewis Lab

Harvard University

125

Rogers Research Group

University of Illinois

Zheng Research Group

Stanford University

Shlomo Magdassi Group

Hebrew University of Jerusalem

Flexible and Nanobio Device Lab


(FAND)

Koreas Advanced Institute for


Science and Technology

Flexible Energy and Electronics


Laboratory
Advanced Flexible Electronics
Laboratory

University of Toronto

Complex uids, colloidal assembly


and printing of functional materials
Bio-inspired/bio-integrated
electronics, solid state lighting and
photovoltaics, semi-conductor
nanomaterials and carbon
transistors
Transfer printing methods for
exible electronics
Conductive inks: metal
nanoparticles and carbon
nanotubes, coatings, and inkjet
printing
Flexible energy sources, exible
optoelectronics, exible electronics
and laser material interaction
Electrochemical energy storage and
printed organic memories
Thin lm devices, printed
electronics and exible/stretchable
electronics
Integrated circuits, exible
AMOLED displays, interactive
electronic skin, printed electronics
and high speed exible RF
transistors
Wearable e-textiles for wireless
health monitoring, exible solar/
battery nano-textile, nanowire
growth and device fabrication,
exible organic solar cells, exible
transistors and circuit fabrication
technology and modeling of
nanomaterials and nanocomposites
Devices on plastic, sensors, exible
circuits, unusual substrates and
smart textiles
Printed and exible energy
harvesting devices, printed and
exible energy storage, devices,
printed large-area antennas, printed
large-area electronics, printed largearea optoelectronics, printed
sensors, wearable medical devices
Exploration of functional materials,
innovative printing processes and
microscopic evaluations

Seoul National University

Flexible Electronics Group at MSU

Michigan State University

Flexible Electronics and Energy Lab


(FEEL)

University of British Columbia

Electronics Laboratory-Wearable
Computing

Swiss Federal Institute of


Technology, Zurich

Arias Research Group

University of California, Berkely

Flexible Materials Base Team

The University of Tokyo

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126

127
128

129

130
131

132

133

134

135

136

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expensive exible devices based on ITO, graphene, silver and


CNT electrodes is a tougher job but there is a chance of integrating copper-based conductive patterns in these devices by
fabricating them in an inert atmosphere. Research into
controlling the oxidation problem in copper-based inks should
also be done.
The automotive sector has a huge demand for MEMS devices
that are based on physical lithographic techniques as well as
conductive inks. Inexpensive copper ink has the capability to
replace expensive silver-based, graphene and CNT inks by
overcoming its drawbacks. Some of the future technological
aspects where copper ink can be integrated are explained in
detail below.
Self drawing biosensors:117 University of California
researchers developed a biocompatible enzymatic ink-based
roller pen which is phenol-sensitive (Fig. 115). To this ink,
they added some conductive additives like graphite powder for
sensing purposes. They also claim that the strips used for
sensing are re-usable. The group is presently working on wireless self drawing sensors and their analysis over various
extremes of conditions like temperature, humidity and
sunlight.
Articial ophthalmologic implants124 are one of the most
important aspects for vision defective people. Research into
contact lenses for suppressing color-blindness is on the way.
Copper-based conductive ink instead of gold can be incorporated for electrical interconnections in these ophthalmologic
implants because of its antibacterial and antifungal properties
(Fig. 116).
Apart from the aforementioned applications, solar-powered
wearable trackers, pain relief skin patches, dermatological
implants, exible touch screens, etc. constitute the most anticipated applications.

11. Research groups working in the


area of exible devices125136
All over the world many research groups are actively participating in the fabrication of exible devices. Some of the most
prominent research groups are mentioned in Table 2.
Apart from the mentioned research groups, many other
groups all around the world are working on this technology.
Many government-funded laboratories are also actively participating in the research of exible electronic devices as it is the
most awaited technology of the future.

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

This journal is The Royal Society of Chemistry 2015

nanoparticles. However, only a few have been successful in


formulating them into conductive inks and conductive
patterns. LI Song, LI Luhi, F. Xiao, Chen, W. Yang, etc. have
formulated conductive inks. Apart from chemical reduction,
pulsed vapor deposition, photochemical synthesis, particle-free
conductive ink, graphenecopper nanocomposites, transparent
electrodes, nanoparticle/nanowire suspensions, etc. were also
used for successful formulation of conductive inks, as discussed
above. We hope that this review serves as a good source of
knowledge for researches who are interested in conductive inks
and their applications. We have discussed in brief the synthesis
and challenges of the present technology of exible electronics
via copper inks. The next era of technology depends on exible
electronics and hence we present this review as a stepping stone
for the future.

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.

Notes and references


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