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Mechanism of Copper(I1) Reduction by
Formaldehyde Studied by On-Line Mass
Spectrometry
Cu2++ 2CD,O
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)
cu
0743-746319212408-1230$03.00/0
cu
+ 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.
I(D2+) I(HD+)/2
I(H:)
+ I(HD+) + I(D:)
100
+ 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.
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
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
initiating the electroless plating because of membrane permeability changes during copper deposition.
+ 40D-
cu
Cuo + 2HC00-
+ 2D,O + H,
(1b)
and reaction of anodic formaldehyde oxidation may be
written as