Materials Letters 61 (2007) 1125 – 1129

www.elsevier.com/locate/matlet

Preparation of fine copper powder using ascorbic acid

as reducing agent and its application in MLCC
Songping Wu
College of Chemistry, South China University of Technology, Guangzhou 510641, China
Received 9 January 2006; accepted 25 June 2006
Available online 20 July 2006

Abstract

The preparation of ultrafine copper powder with chemical reduction method was investigated. Ascorbic acid was employed as reducing agent.
Reaction of CuSO4·5H2O with ascorbic acid at 70 °C gives polyhedron monodispersed ultrafine copper powder. The copper powder having
excellent dispersibility was prepared when the pH value was controlled at 6 with aqueous ammonia. Influences of reaction temperature on the
efficiency of copper powders were also studied. TG/DTG/DTA of copper powder was discussed with thermal analyzer. As-prepared copper
powder was applied in BME-MLCC. The micro-structures of end termination and interface were discussed with SEM and polarized light
microscope. The copper end termination has high adhesion force, excellent solderibility behavior and resistance behavior to soldering.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Fine copper powders; Chemical reduction; Ascorbic acid; MLCC

1. Introduction
Recently, an increasing interest has been found in synthe-
sizing nanoscale particles and cluster [1,2]. Ultrafine metallic
powders are commonly used in electrically conductive paste,
solid oxide fuel cells and chemical catalysts, etc.
In the manufacture of electronic devices, such as hybrid
integrated circuits and multilayer ceramic capacitors, the tech-
nology of making conductive thick films from metal powders is
of considerable importance. Base metal electrode multilayer
ceramic capacitors (BME-MLCCs) are seen as a more
economical alternative to the conventional precious metal
electrode design. Considerable interest for synthesizing copper
powder has increased during the past few years because of its
high electrical conductivity, relatively higher melting point,
excellent solderability, low electrochemical migration behavior
and low materials cost [3]. For conductive paste application, it is
required to use high purity crystalline non-agglomerated copper
powder, which is free from surface oxidation [4,5]. The vapor
phase process is a widely employed method of producing metal
powder, such as copper and nickel [3,6]. Various reducing agents
E-mail address: chwsp@scut.edu.cn.
0167-577X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.06.068
like hydrazine [7], glycerol [8], etc., have been used for the
production of copper powders.
In the paper, we report a chemical reduction method as a
processing technique for the formation of copper particles with
excellent dispersibility and study its application in BME-MLCC.
2. Experimental
All chemicals of reagent grade quality were used without
further purification. Copper powder was obtained by reaction
of copper sulfate pentahydrate with ascorbic acid. In a typical
preparation of copper powder, 1000 ml solution containing
300 g CuSO4·5H2O and dispersion agent was added during
40 min to a stirred 2800 ml solution containing 250 g ascorbic
acid. Aqueous ammonia was employed to control pH value.
The temperature was kept 50 °C–70 °C for 2 h to carry out the
reaction sufficiently, to reduce copper ion in the solution to
metallic copper. The metallic copper powder was recovered
from the solution, washed and dried under vacuum.
Resin, copper powder and glass were mixed to prepare a
thick film paste containing 60–70 wt.% copper. After rolled
several times by a three-roll mill, the paste was coated on the
termination of chip (0805 Y5V) and dried, then, the copper end
terminations were fired at 915 °C for 10 min in a nitrogen
1126 S. Wu / Materials Letters 61 (2007) 1125–1129

Table 1
Influence of temperature on efficiency
Temperature/°C pH Efficiency/%
1 30 5 < 20
2 30 7 < 20
3 30 9 < 20
4 53 6 85
5 60 6 88
6 70 6 92

Fig. 1. XRD spectrum of copper powders.
atmosphere, with a controlled level of oxygen, to obtain
BME-MLCC.
Direct observations of the powder and copper end termina-
tion were made by scanning electron microscopy (SEM) on a
XL30δDX-4i (Philips), to reveal the shape of the particle, their
diameter and size distribution. The mean sizes and dispersibility
of the powder were estimated from the image analysis of the
laser size distribution analyzer (LS230). The crystal structure
was characterized by X-ray diffraction. Thermal analysis of the
copper powder was carried out at scanning rates of 10 °C/min in
a flowing air atmosphere. BME-MLCCs were fixed with resin
and processed with a grinding and polishing machine. The
connection of internal–terminal electrode and distribution of
glass in termination were observed with polarized light micro-
scope (Olympus BX51M). The adhesion strength of the elec-
trode was determined with FDV-50 force apparatus (Wagner
Instruments, USA).
nuclei will result in the too small particle, which is easily oxidized. If
the reaction rate is too slow, it is very difficult to prevent the powder
from coming together. Hydrazine hydrate and formaldehyde were
widely used as reducing agent to prepare ultrafine powders. However,
in this system, the reducing power of hydrazine hydrate or formal-
dehyde is too strong to obtain uniform and monodispersed copper
powder. Reducing sugar was also employed to produce metallic pow-
der, such as copper powders, nickel powders and copper–nickel alloy
powders. However, to obtain copper powder, high reaction temperature
is needed due to the weak reduction power of reducing sugar. Because
of middle reduction power, ascorbic acid was chosen as the reducing
agent in my work. In the course of the reaction, the addition of
dispersed CuSO4 droplet into the dispersed ascorbic acid is important
that a confined amount of copper ion in a droplet of CuSO4 may govern
the size of copper powders. In the absence of a dispersion agent, it is

3. Results and discussion

3.1. Basic chemical reaction and choice of reducing agent

In this work, pH value was controlled by adding appropriate amount

of aqueous ammonia. Copper sulfate pentahydrate reacts with aqueous
ammonia to obtain Cu(OH)2 according to reaction (2), Cu(OH)2 was
reduced to obtain fine metallic powder as being seen in Eq. (3). In this
process, the following chemical reaction occurred.

Cu2þ þ C6 H8 O6 →Cu þ C6 H6 O6 þ 2Hþ ð1Þ

Cu2þ þ 2OH− →CuðOHÞ2 ð2Þ

CuðOHÞ2 þ C6 H8 O6 →Cu þ C6 H6 O6 þ 2H2 O ð3Þ

The formation of “monodispersed” particles could proceed through

a two-stage mechanism. The primary particles are produced first, which
then aggregate to larger final products. There are two possible
mechanisms involved in the aggregation, based on either diffusion-
limited or reaction-limited processes. The subunits have to overcome
energy barriers to effectively collide with growing particles [9]. If the Fig. 2. SEM photographs of ultrafine copper powder obtained at different pH
reaction rate is too fast, rapid formation of a large amount of copper value, 1 — pH 2.2 and 2 — pH 6.
 S. Wu / Materials Letters 61 (2007) 1125–1129
Fig. 3. Size distribution pattern of copper powders.
possible that monodispersed particles tend to grow once copper ion
remained in the solution.
To prepare fine powder with the chemical reduction method, it is
very important to choose an appropriate dispersion agent. Generally
speaking, a dispersion agent absorbs on the solid–liquid interface and
forms a layer molecular membrane to hinder inter-contact between the
particles. At the same time, it will reduce surface tension, thereby
reducing the absorption capability of the capillary. In this work, the
water-soluble polymer surfactant, such as gelatin, was employed as the
dispersing agent.
Fig. 1 showed the XRD pattern of the product prepared by the
solution containing CuSO4·5H2O and ascorbic acid. From the pattern,
one sees that the diffractogram exhibits the characteristic peaks of
crystalline metallic copper (fcc) d = 2.0897, 1.8091, 1.2790, respec-
tively, which is very close to that given by JCPDS file no. 4-836
(d = 2.088, 1.808, 1.278).
3.2. Effect of reaction temperature
The reductive power of ascorbic acid depends on the reaction
temperature greatly. The efficiencies of copper powders at different
temperatures are listed in Table 1. As seen from these data, it is clear
that the efficiency is stable and low to 20% in spite of the increase in pH
value when the reaction temperature is lower than 50 °C. When the
reaction temperature is more than 50 °C, the efficiency increases as the
reaction temperature increases up to 92% at 70 °C.
3.3. Effect of pH value
Influence of pH value on the reduction power of ascorbic acid is
obvious. According to Eq. (4), the potential decreases with an in-
creasing pH value, and it shows the increase in reduction power of
ascorbic acid.
C6 H6 O6 þ 2Hþ þ 2e ¼ C6 H8 O6 E0 ¼ 0:08 VðpH ¼ 6:4Þ
0:059
E ¼ E0 þ 1g½Hþ 2
2
E ¼ E0 −0:059 pH ð4Þ
The existing state of copper ion and the reduction power of ascorbic
acid depend on the pH value in aqueous ammonia media. Influences of
the pH value on powder particles were investigated as follows.
1127
Fig. 2 showed the SEM photos of the ultrafine copper powders
prepared at pH 2.2, as given in Fig. 2.1, and at pH 6, as given in Fig. 2.2,
respectively. The following salient features of these powders are
observed: (1) the powder particles are polyhedral, non-agglomerated
monodispersed, and (2) their diameters are uniformly distributed below
2.7 μm for samples prepared at pH 2.2. When the pH value is up to 6,
and the CuSO4·H2O solution and aqueous ammonia were simulta-
neously added at 60 °C, a large amount of red powders was obtained in
a few minutes. The particles are of uniform size of 1.5 μm. The
difference of particle size under different pH value can be explained as
follows:
(1) When the pH value is 2.2, CuSO4 was reduced to obtain fine
metallic powder according to Eq. (1). A high concentration of
Cu2+ increases the aggregation of copper atoms and particles,
and it results in an increase of the average particle size of the
copper powder. However, when the pH value is 6, CuSO4 was
change into Cu(OH)2, and was reduced according to Eq. (3). A
low concentration of Cu2+ decreases the average particle size of
copper powders. It was reported [1] that particle size of metallic
powders increases with an increasing concentration of metallic
salt, which is in agreement with our observation.
(2) The reducing power of ascorbic acid is pH-dependent. In our
other work [10], silver nitrate was reduced with ascorbic acid to
obtain ultrafine silver powders, whose size decreases with
increasing pH value. It is very similar to recent work.
Fig. 4. Influence of pH value on efficiency.
1128 S. Wu / Materials Letters 61 (2007) 1125–1129
Fig. 5. Thermal analysis of the copper powder.
Copper powder particles prepared from the solution having a pH
value of 6 are perfect polyhedron, and have uniform size and narrow
particle distribution as shown in Fig. 3. The average congeris size (D50)
and standard deviation of polyhedral particles of copper was 3.9 μm
and 1.5 μm. The experimental particle size distributions show excellent
symmetry.
Ultrafine copper powder, which has large specific surface area and
large surface energy, can dissolve rapidly in weak acid or aqueous am-
Fig. 6. SEM photographs of copper end termination.
monia solution. The efficiency is shown in Fig. 4, in which the efficiency
of copper first increases, then decreases, with increasing pH value. There
is a largest efficiency at pH value of about 6.
3.4. Thermal analysis of the powder
Metallic copper deposited by the above method was analyzed by TG/
DTG/DTA in an air flow with a heating rate of 10 °C/min. This is
demonstrated in Fig. 5, where the weight gain of the copper powder is
given as a function of temperature. From Fig. 5, we can see that the
temperature at which oxidation or weight gain becomes significant is
greater than 237 °C for copper, and the weight increases steady up to
500 °C. Above this temperature, the level of the cupric oxide formed is
reached. The gain in oxygen at 600 °C was 24.3 mg per 100 mg which
corresponds to the oxidation of copper to cupric oxide on heating.
3.5. Copper end termination of BME-MLCC
Appropriate resin, ratio of spherical copper and flake, and glass,
which is stable under high firing temperature and a nitrogen atmo-
sphere, acid resistance and good wettability to the selected copper
powders, were chosen to prepare a thick film paste. The paste having
excellent rheology behavior was rolled several times by a three-roll
mill to destroy the soft agglomeration of copper powders. Copper end
Fig. 7. Polarized light photo of a section of MLCC.
 S. Wu / Materials Letters 61 (2007) 1125–1129
terminations were fired at 915 °C for 10 min in a controlled nitrogen
atmosphere. The SEM photos of copper end termination were given in
Fig. 6. The connection between internal electrodes and end terminal
electrodes was excellent as given in Fig. 6.1. Wetting and interface
reaction in lead borosilicate glass–precious metal systems have been
studied by Nagesh et al. [11]. They reported that increasing wetting or
decreasing contact angle could be attributed to interfacial reactions. A
sharing of oxygen with a continuity of electronic structure across the
interface (chemical bonding) causes a reduction in the interfacial
energy and strong adhesion. It was reported that the rough glass–metal
interface or porous micro-structure occurs in the interface of the elec-
trode and chip due to the interface reaction [12,13]. The termination of
green chip was very smooth due to being processed by a cutting machine.
However, the interface becomes rough and porous, as shown in Fig. 6.1,
after copper terminations of BME-MLCCs were fired. It means that
interfacial reaction occurs. Our observation is in agreement with other
studies. The proper attachment of the glass to the dielectric bodies
produces adhesion of the end termination to the chip. The adhesion
strength is high because of this attachment and excellent connection of the
internal–terminal electrodes. The average adhesion strength of the elec-
trode is 6.8 lb.
As seen in Fig. 6.2, the densification of the fired end termination is
good and the smaller apex-to-side ratio of the end termination means
larger termination coverage. The so-called blister problem, in which
blisters occur between the dielectric body and the end termination, does
not occur. 95% of the terminal electrode covered by a new solder shows
that MLCC has excellent solderability behavior. Resistance behavior to
soldering is tested at 260 ± 5 °C, and 80% of the terminal electrode is
covered by a new solder.
3.6. Polarized light microscope study
The BME-MLCC was processed with a polishing machine. The po-
larized light microscope was employed to investigate the connection
between internal–terminal electrode, distribution of glass and interfacial
layer. The cross-section photograph of BME-MLCC was shown in Fig. 7.
One can see that the connection of internal–terminal electrode is very
obvious, and the distribution of glass (light red), as seen in Fig. 7, is even in
termination. A gray bond, which may act as an important role in supplying
adhesion strength, occurs between the termination and chip. The gray
bond can be reasonably explained as the result of interfacial reaction.
Because interfacial cracks, which are believed to be the result of the
thermal expansion mismatch between the reaction bond and chip, may
result in the decrease of adhesion strength and failure of the component,
and so the suitable firing temperature was employed. Therefore the
reaction bond in this work is very thin (about 2 μm), implicating a low
residual tension stress between reaction bond and chip, which was
demonstrated to grow with the thickness of the reaction layer [11].
1129
4. Conclusions
In conclusion, we have synthesized highly pure, polyhedron
non-agglomerated monodispersed copper powders by the reaction
of CuSO4·5H2O and ascorbic acid in appropriate pH value and
reaction temperature. The XRD of the as-prepared copper indi-
cated that an fcc crystalline copper was directly formed by the
chemical reduction method. Copper particles of polyhedron shape
and uniform in size were formed. The copper end termination of
BME-MLCC prepared by the as-prepared copper has excellent
solderibility behavior, resistance behavior to soldering and high
adhesion force due to excellent connection of the internal–ter-
minal electrode and termination electrode–chip.
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