1998 IEW/IMC Proceedings

EFFECTS ON ETCHING RATES OF COPPER IN FERRIC CHLORIDE SOLUTIONS

Cai Jian , Ma Jusheng, Wang Gangqiang, Tang Xiangyun

Department of Materials Science & Engineering, Tsinghua University, Beijing 100084

ABSTRACT

Influences of several factors on etching rates of Cu in FeCl3 etchant are studied with a spray
etching apparatus in this paper. The etching surfaces of Cu are analyzed by XRD and it proves that there is a
CuCl passitivation film on the etching surface. A brief explanation is offered based on the relationship
between etching rate and etching time. It indicates that cations influence the etching rate as the effects of
different chlorides on etching rates have been studied. Additionally, the quantity of copper dissolved in FeC13
etchant and regeneration of spent etchants are also investigated in this paper.

INTRODUCTION used for etching of copper alloy [3]. Due to the

Lead frame is one of the important components
in microeletronic packaging. It provides electric
connects between chip and the outer. Additionally,
it provides mechanical supporting and thermal
dispersal. Lead frames are developing to multi-leads
and fine pitch when electronic packaging is
developing to smaller, lighter and thinner. Forming
of lead frames has become a more important issue
in electronic packaging. Commonly, there are two
methods of forming of lead frames which are
stamping and photochemical etching [ 1,2]. As far as
multi-lead frame is considered, photochemical
etching has some advantages such as flexibility,
small scale and short product cycle compared with
stamping.
Materials used in manufacturing lead frames
are Kovar alloy, Iron-Nickel alloy and copper alloy.
In recent years, Iron series alloy is also developed.
In ceramic packaging, Iron-Nickel alloy has taken
the place of Kovar alloy as the major lead frame
material due to lower price. But in plastic packaging,
copper alloy is mostly used for lead frame. Solution
used in photo-chemical etching of lead frames are
FeC13 solution and CuC12 solution. Usually, FeC13 is
used for etching of Iron-Nickel alloy while CuCI2 is
advantages of low price and quick etching rate and
using the same solution for etching Iron-Nickel
alloy and copper alloy, etching of copper in FeC13
solution is studied in this paper and the etching
mechanism is briefly analyzed.
EXPERIMENT PROCEDURE
The etching of copper is performed in a spray
apparatus, which consists of a nozzle, a magnetic
bump, bathes and some tubes. Copper in this study
is 99.7% purity. FeC13 solution is obtained by
dissolving the FeClp6H20 powder(chemica1purity)
in deionized water. The concentration of FeCl3
solution is 2SM(33"Be'). The temperature in
experiment is 25 'C and the volume of solution is
500ml.
The etching rate is denoted by pm/min which
is converted from weight loss. Etching rates of
copper in CuC12 and FeC13 solutions are compared.
Some factors, e.g. etching time, the quantity of
copper dissolved in etchant and various chloride
additives are researched. The regeneration of spent
solution is also investigated.

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 RESIJLT OF EXPERIMENTS
1)Etching rates of Cu in FeC13 and in CuC12
solutions
The comparison of copper etching rates in
FeC13 and in CuiC12 solutions is shown in fig.1. The
concentration of FeC13 is from 15 to 48"Be', while
CuC12 is from 15 to 50"Be', at etching time of 3
minutes. The etching rates have similar trends
versus concentration of FeC13 and CuC12 solutions.
Fig 1 ]EtchingRate in Different Etchants
There exists a imaximum etching rate in a certain
concentration. The etching rates of copper in FeC13
etchant is 3 to 4 times greater than in CuC12 etchant.
2) Trace of etch:ingrates with etching times
The trace of etching rates with etching times is
shown in fig.2. Value of etching rate is a average
value in etching time. As shown in fig.2, the
0 6 ;o ' lbo ' 150 ' & ' $0
etching time@)
Fig 2 Etching Rates Versus Etching Times
relationships between etching rates and etching
times in etchants with different quantities of copper
dissolved are similar. The etching rates decreases
rapidly when etching time is less than 60s. When
etching time exceeds 60s, etching rate decreases
very slowly.
3)Effects of quantities of copper dissolved in
etchants on etching rates
20-
5#E
P
15 >\
-
\ 'O
3 L
5 " " ' ~ ~ O
Fig. 3 Etching Rate Versus Quantity
of Copper Dissolving in Etchant
A good etching solution must have the ability
to dissolve large quantity of copper because its
etching ability decreases with the dissolution of
copper in it. Fig.3 shows the tendency of mean
etching rate with quantity of dissolved copper in
etchant.
It shows that etching rates is still at a static
high value when the quantities of copper dissolved
are less than 20g/l. Then etching rates decrease as
the quantities of copper increase. When the
quantities is more than 60g/l, the etching rate tends
to keep constant which corresponds to the half of
the maximum.
4)Influence of additions on etching rate
As shown in fig.4 and fig.5, the influences of
' I different additions, including chlorhydric acid,
kalium chloride and sodium chloride on etching
rates are also investigated. It indicates that addition
of chlorhydric acid has weak effects on etching
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rates. The etching rates of copper increases Sodium chlorate is selected as a regenerate
obviously as kalium chloride is added in. And when reagent. By addition of sodium chlorate, the etching
the kalium chloride added in attained 0.8-1.2M, the rates of copper in spent etchant will be regenerated.
etching rate reaches a maximum which is 25% Finally, the etching rates will reach a 80% value of
higher than that without kalium chloride added in. fresh etchant.
When kalium chloride is added continually, etching
rate goes down. However, addition of sodium ANALYSIS AND DISCUSSION
chloride results in decrease of the etching rate.
When the addition of sodium chloride is more than In the experiment a porous film formed on
1.2M, etching rate will keep constant about 80% of copper surface after etching has been observed.
that without sodium chloride additive. There are some reports about passivation film
formed on copper surface in acidic media [4,5,6]. A
small angle X-ray diffraction is used to analysis and
the XRD spectrum is shown in fig.6. Three stronger
7 peaks marked as 4,6,9 correspond (1 1l), (200) and
(220) crystal planes of copper, which interplanar
distances are 2.09, 1.8 1 and 1.28 angstrom. Another
three peaks marked as 1, 2, 5 with interplanar
distance of 3.13, 1.82 and 1.62 angstrom
2E1 "
to
"
20
"
30
"
40
"
50
' respectively, correspond three crystal planes of
quantities of chkxhylric azd CuCl. This confirms that the film formed on the
added into 503 ml solution(m1)
copper surface is CuCl.
Fig 4 Influence of chlorhydric acid
on etching rates

6 -

. +

o
KU
w

2"W 012 ' d1 ' dE ' dS ' 4'0 112

quantities of chlorides added in 500ml solubon(m0l)

Fig 5 Influence of different chloride Fig 6 XRD spectrum of Cu etching surface

on etching rates

5)Regeneration of spent etchant The initial product of copper etching in FeC13

The etching ability of etchant will drop down solution is CuClj2-. On the one hand, CuC132-will
as copper dissolved in it. In this experiment, etching be oxidized to Cu2+by diffusing to the bulk solution.
rate which decreases to a 50% value of fresh etchant On the other hand, the CuC1:- which has not
is assumed to be the spent etchant. It corresponds to diffused to bulk solution will deposit on the etching
the quantity of copper dissolved to 60g/l in etchant. surface as CuC1. They may be described as:

146
 Cu + Fe3++ 3C1- = CuC1:- + Fe2+
(on etching surface) (1)
C U C ~+~Fe3+ ~ ' = Cu2' + Fe2++ 3C1-
(in bulk solution) (2)
cuc132-= CUCl(.l) + 2c1-
(on etching surface) (3)
In fig.2, it is associated with the CuCl film that
within 60 seconds etching rate dramatically
decreases with etching time and then decreases very
slowly. As wc: know, etching of copper in FeCl3
solution is controlled by diffusion, consisting of
Fe3+diffuses from bulk solution to copper surface
and by-prodwcts from etching surface to bulk
solution. The forming of CuCl passivation film
leads to the decrease of etching rates with etching
times. When the original copper surface contacts
with the etchant, the etching rate is the maximum
due to no CuCl film on the surface. Then, in initial
etching the CuCl film, a diffusion barrier, forms on
the copper surface. To continue etching, the Fe3+or
by-product C U C ~must ~ ~ 'go through the film, which
makes a slow etching. That is why the etching rate
deceases rapidly. At the same time, the tendency of
etching rate dlecreases slowly associating the film
grows thicker.
The influence of quantity of copper dissolved
in the etchant on etching rate is shown in fig.3.
According to equation (l), (2), dissolution of
copper in FeC13 solution will reduce the
concentration of Fe3+ and generate Fe2+and Cu2+,
which means tlhat the copper specimen will not only
be etched by Fe3+but Cu2+and its etching rate is a
sum from Fe3' and Cu2'. As we know, etching of
copper in CuC:12 solution (providing Cu2+)is much
slower than in FeC13 solution (providing Fe3+).
Therefore, for a little quantity of copper dissolved
in FeC13 solution, Cu2+may offset the decrease of
etching rate from Fe3+ partly. As a result, the
etching rate has no obvious variation. When the
quantity is gre:ater, the compensation is no longer
enough so the: etching rate goes down with the
quantity.
147
According to equation (3), the precipitation of
CuCl will be inhibited if the concentration of C1- is
increased. Chrohydric acid (HCl), kalium chloride
(KCl) and sodium chloride (NaCI) have been added
into etchants to investigate their influences on
etching rates. Experiment shows that addition of
KCI increases etching rates, HCI has rarely effects
on etching rates but addition of NaCl has negative
effects on etching rates. This indicates that C1- is not
the only one influence factor of etching rates and
the kind of cations should have some influence too.
Theoretically, the major reason of etchant's
failure is Fe3+has been reduced to Fe2+ when Cu
oxidized to Cu2+.This has also been obtained in the
case of Iron-Nickel alloy etching. Sodium chlorate
will oxidize Fe2+to Fe3+as it is a strong oxidant. In
our experiment, the etching rate has been
regenerated to a 80% value of fresh etchant. The
reason of that has not been regenerated completely
is flexibility as the increasing of etchant Baume has
been ignored. Another reason is the production of
sodium chloride in etchant.
CONCLUSION
Etching process of lead frames is simulated in
this experiment. The influences of some factors on
etching rates have been studied with a spray
apparatus.
1)The etching rate of copper in FeC13 is more
greater than in CuCl2 solutions.
2)The passivation film formed in etching
process is CuCl. The forming of this CuCl film is
the reason to dramatically decrease of etching rate
within 60s.
3)Not only C1- but also cations will affect the
etching rate of copper.
4)When the quantity of copper dissolved in
etchant attain to 60g/l, the etching rate drop to the
50% of fresh etchant. The additive sodium chlorate
will regenerate the spent etchant.
 REFERENCES

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Technology), 1996,36(Sl), 30-35.
(3) Allen D M, “The Principle and Practice of
Photochemical Machining and Photoetching” ,
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