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1230

Langmuir 1992,8, 1230-1231

Notes
Mechanism of Copper(I1) Reduction by
Formaldehyde Studied by On-Line Mass
Spectrometry

Cu2++ 2CD,O

Zenonas Jusys' and Algirdas Vagkelis


Institute of Chemistry and Chemical Technology of
Lithuanian Academy of Sciences, Goitauto 9,
232600, Vilnius, Lithuania
Received April 16, 1991. In Final Form: October 22, 1991

Introduction
The main reaction of the widely used electroless copper
plating process is the autocatalytic reduction of copper(11) ions by formaldehyde. A somewhat unusual feature
of this reaction is the formation of molecular hydrogen
along with the metallic copper. The reaction stoichiometry as determined in' and confirmed by other researchers
in a simplest form (taking into account neither the
formation of methylene glycol and the dissociation of it
in alkaline medium nor the chelation of Cu2+ in the
presence of complexing agent) may be expressed as
cu
Cu2++ 2CH,O + 40H- Cuo + 2HC00- + 2H,O + H,

(1)

The mechanism of this reaction is assumed by most of


the researchers to be an electrochemical one: two partial
reactions, anodic oxidation of formaldehyde
cu
2CH,O + 40H- 2HC00- + 2H,O + H, + 2e- (2)
and cathodic reduction of Cu(I1)
cu
CU'+ + 2eCuo
(3)
are expected to proceed simultaneously on the copper
surface, with electrons being transferred via metal. The
electrochemical mechanism was proved experimentally
in the 1960~,-~by means of electrochemical modeling of
reaction 1. Later studies showed the above electrochemical
half-reactions to interact; i.e., the acceleration of cathodic
copper deposition by anodic formaldehyde oxidation was
found to take place together with the acceleration of the
latter by copper cathodic reductiona5t6
The origin of hydrogen evolving in reactions 1 and 2
could be determined using a deuterium tracer. Using the
isotope labeling, hydrogen was found to evolve entirely
from the C-H bond of formaldehyde during the anodic
oxidation of it on ~ i l v e r .Thus,
~
formaldehyde anodic
oxidation on Cu may be expected to proceed by

cu

2CD,O + 40H- 2DC00- + 2H,O + D, + 2e- (2a)


The overall reaction of copper reduction by formaldehyde
in this case should be as follows:

0743-746319212408-1230$03.00/0

cu

Cuo + 2DC00- + 2H,O

+ D,

(la)
However, the gas evolved during electroless copper
deposition in CD2O solution was determined in the recent
worke to contain more than 99 96 of HD. The mechanism
was suggested,8which explained the hydrogen formation
in equal parts from formaldehyde and water. Therefore,
a further investigation of electroless copper deposition is
necessary. It seemed to us of great interest to apply an
on-line mass spectrometric analysiss for studying this
process under various conditions in the range of real electroless copper plating solutions, including also those of
ref 8. The feasibility of differential electrochemical mass
spectrometry (DEMS)lO for investigating the formaldehyde anodic oxidation on Au electrode was demonstrated
in the recent work."
Experimental Section
Solutions and Materials. Two series of experimental runs
were carried out in electroless copper plating solution, containing
(mol L-') CuS04(0.04), EDTA (0.04), and CDzO (or CH20) (0.08)
a t pH 12.0 or 12.5 and t o = 20 or 70 "C. One of them contained
deuterated ("heavy") formaldehyde (CDzO) (deuterium content
98 mol % ) as a reducing agent, while "light" water (H20) as well
as other materials including light hydrogen was used. The other
contained CH20 and D20 (D content 99.8 mol 72 ) as a solvent
as well as water-free salts of CuSO4 and tetrasodium ethylenediaminetetraacetate; pH was adjusted with NaOD (Dcontent 99
mol 5%) in this solution. In both cases paraformaldehyde was
used for the solution preparation. Solutions were deaerated with
Ar.
Analysis of the Evolved Gas. A mass spectrometer MI1201 (USSR) was used for the conducting isotopic analysis of the
gas evolved, which was sucked through a porous Teflon membrane
(thickness 5 pm) into the ion source of the mass spectrometer
and detected on-line. Electroless copper plating was carried out
on the outer side of the membrane covered with a -0.1-pm copper
layer sputtered in vacuum (the geometric area of 1 cm2). Electroless copper plating was initiated by a cathodic switch of potential to -0.6 V (vs Ag/AgCl/KCl saturated electrode) for 1-2
S.

The experimental setup used for the on-line mass spectrometric


gas analysis was the same as in ref 12.
Deuterium content was calculated by the equation
Dmol% =

I(D2+) I(HD+)/2
I(H:)

+ I(HD+) + I(D:)

100

where I(Hz+), I(HD+), and I(Dz+) are mass intensities of Hz+


(m/z = 2), HD+ (miz = 3), and Dz+ ( m / z = 4) (PA). Other volatiles had been cooled with liquid nitrogen before the gases
reached the ion source of the mass spectrometer.
Isotopic gas composition had been measured on 3-5 copper
electrodes for 20 min, and the mean value was calculated. An
accuracy of mass spectrometric analysis depended on mass
intensities and was ranging from *0.2 to f0.5 mol % . The values
of mass intensities presented were detected immediately after
(8) Ogura, T.; Malcolmson, M.; Fernando, Q. Langmuir 1990,6, 1709.
(9) Bruckenstein, S.; Gadde, R. R. J . A m . Chem. SOC.1971, 93, 793.
(10) Wolter, 0.;Heitbaum, J. Ber. Bunsen-Ges. Phys. Chem. 1984,88,

(1) Lukes, R. M. Plating 1964, 5 1 , 1066.


(2) Saito, M. J . Met. Finish. SOC.J p n . 1965, 26, 300.

(3) Vaikelis, A.; Salkauskas, M. Liet. T S R Mokslu Akad. Darb. 1967,


8 4 (51), 3.
(4) Paunovic, M. Plating 1968, 5 5 , 1161.
( 5 ) VaHkelis, A.; JaEiauskiene, J. Elektrokhimiya 1981, 17, 1816.
(6) Wiese,H.; Wei1,K. G . B e r . Bunsen-Ges.Phys. Chem. 1989,91,619.
(7) Hoyer, H. 2. Naturforsch. 1949, 4a, 335.

+ 40H-

2.
(11) Baltruschat, H.; Anastasijevic, N. A.; Beltowska-Brzezinska, M.;
Hambitzer, G.; Heitbaum, J. Ber. Bunsen-Ges. Phys. Chem. 1990, 94,
996.
(12) Jusys, 2.; Liaukonis, J.; Vaikelis, A. J . Electroanal. Chem. 1991,
307. 87.

0 1992 American Chemical Society

Langmuir, Vol. 8, No. 4, 1992 1231

Notes
Table I. Mass Intensities of I&+, HD+,and Dz+and
Isotopic Composition of Gas Evolved during Electroless
Copper Plating.
expt
no.
~

2
3
4
5
6
7
8

DH
12.0
12.0
12.5
12.5
12.0
12.0
12.5
12.5

t.OC
20
70
20
70
20
70
20
70

I(Hz+), I(HD+), I(Dz+),


uA
MA
LLA
9.30
0.04
0.34
1.00
24.50
0.15
17.25
0.10
0.60
46.00
0.30
2.00
0.04
0.00
9.30
0.01
24.75
0.06
0.00
17.80
0.05
0.02
46.10
0.20

D,
mol%
97.8 f 0.5
97.6f 0.3
97.7 f 0.4
97.7 0.2
0.5 f 0.5
0.4 f 0.3
0.4f 0.4
0.2 f 0.2

0 Solution contained (mol L-l) CuSO, (0.04),


EDTA (0.04),and
formaldehyde (0.08). Experiments 1-4 were carried out in H2O
solution containing CDzO (D content 98 mol 5%) and 5-8 in D20 (D
content 99.8 mol % ) solution containing CHz0.

initiating the electroless plating because of membrane permeability changes during copper deposition.

Results and Discussion


Our results showed all the amount of gas evolved during
electroless copper deposition to originate from formaldehyde (Table I). These results were obtained in the
solution containing heavy formaldehyde and light water
as well as in the "mirror" system of light formaldehyde
and heavy water. Isotopic gas composition was determined
to be the same as that of formaldehyde used for copper(I1)
reduction; i.e., no excess of water hydrogen isotope was
detected in the gas as compared to formaldehyde within
the measurement error.
These data are consistent with the electrochemicalmechanism of electrolesscopper plating. In the case when heavy
formaldehyde and light water are used, reaction l a is the
total reaction of anodic and cathodic half-reactions 2a and
3. In the other case, when light formaldehyde and heavy
water are used, reaction 1 may be expressed as
Cu2++ 2CH,O

+ 40D-

cu

Cuo + 2HC00-

+ 2D,O + H,

(1b)
and reaction of anodic formaldehyde oxidation may be

written as

2CH,O + 40D- 2HC00- + 2D,O + H, 2e- (2b)


According to our recent datal3 obtained by DEMS
combined with isotope labeling, anodic formaldehyde
oxidation on copper in Cu(I1)-free solution also results in
hydrogen evolution from formaldehyde alone as could be
expected from reactions 2a and 2b.
It should be noted that anodic formaldehyde oxidation
reaction 2a,b is expected to be not elementary but a
complex one. The most popular reaction scheme14J5
includes a primary step of catalytic formaldehyde dehydrogenation as a result of its dissociative adsorption on
Cu and disruption of C-D (or C-H) bond with the
formation of labile formyl:
cu
DCDO,,
Dad + DCO,,
(4)
Recombination of hydrogen adsorbed causes the molecular hydrogen to evolve. The metastable formyl is
anodically oxidized:
cu
DCO,,
20H- DCOO- H,O e(5)
The data obtained are consistent with this scheme of
reactions.
The data may be concluded to confirm the electrochemical mechanism of electroless copper(I1) reduction
by formaldehyde. However, they are conflictingwith those
of ref 8. Such a disagreement may be explained by the
preparation for analyzing the samples of gas evolved,8
including the gas elution through an iron-coated alumina
column and the conversion of it into water over CuO at
high temperature. Possibly, deuterium exchange with adsorbed light water took place on the iron-coated alumina
prepared apparently in a light water solution. Therefore,
the data obtained may be distorted, and the mechanism
proposed8 on the basis of these data is a doubtful one.
Registry No. Cu, 7440-50-8;CH20, 50-00-0;Hz, 1333-74-0;
CD20,1664-98-8;DzO,7789-20-0.

(13)Jusys, 2.;Vaikelis, A. Submitted for publication in J . Electroanal. Chem.

(14)Meerakker van den, J. E. A. M. J. Appl. Electrochem. 1981,11,


395.
(15)Buck, R. P.; Griffith, L. R. J.Electrochem. SOC.1962,109,1005.