J54 Journal of The Electrochemical Society, 151 ~8! J54-J61 ~2004!

0013-4651/2004/151~8!/J54/8/$7.00 The Electrochemical Society, Inc.

Epoxy Polymer Surface Roughness Modeling Based

on Kinetic Studies of Wet Chemical Treatments
Sam Siau,a,z Alfons Vervaet,a Andre Van Calster,a Ives Swennen,b
and Etienne Schachtb
a
ELIS-TFCG/IMEC and bDepartment of Polymer Materials, Universiteit Gent, 9000 Gent, Belgium

Epoxy polymers are frequently used for constructing buildup layers. Atop the dielectric polymer metal layers are plated by means
of a wet-chemical electroless and/or electroplating process. The adhesion of the plated metal layers to this polymer surface is of
prime importance for reliability of the interconnection. An increase in the roughness of the polymer surface plays an important part
in the adhesion strength of plated metal layers by increasing the total area of interface between both layers. Hence, the evolution
of polymer surface roughness with time due to the chemical treatment is of prime importance for determining the reliability of
interconnections. A kinetic study of wet solution swellers and oxidizers is made, based on atomic force microscopy roughness
measurements. Each chemical or combination of chemical treatments in a certain sequence has its influence on the evolution of
roughness. The evolution of surface roughness also indicates the mechanisms that lead to the formation of roughness on the
surface. Different models are proposed to explain the influence of sweller agents on polymer surface roughness. The kinetics of
roughness formation under influence of swellers is modeled and the bases of the influence of swellers on oxidizing treatments are
examined.
2004 The Electrochemical Society. @DOI: 10.1149/1.1766314# All rights reserved.

Manuscript submitted September 29, 2003; revised manuscript received January 16, 2004. Available electronically July 20, 2004.

Improvement of interconnection technology is essential for al-
lowing increased signal frequencies and higher density of functions
for future electronics. In order to meet the necessary improvements,
sequential high-density buildup layers and microvia technology
have been developed ~Fig. 1!. This research started in the late
1990s.1 A wiring density of 100-150 mm, defined as the sum of the
width and the distance between copper interconnections ~e.g.,
wires!, is required in order to be able to mount unpackaged chips on
the boards, through flip chip or wire bonding.2
Most of the printed circuit boards ~PCBs! used today are fabri-
cated with a glass-epoxy resin on which metals ~usually copper! are
plated and patterned in order to realize interconnections between
different components placed on top of the substrate. A good adhe-
sion between the copper and the polymer is of prime importance for
reliability of the interconnection.3 By chemical treatment of the sur-
face the characteristics ~physical and chemical! of it can be changed
in order to improve adhesion. It is obvious that the surface proper-
ties of the polymer are important for adhesion of the metal to the
polymer. Hence, there is intense recent research into improving the
adhesion of plated copper onto polymer surfaces. Many processes
involve Ar plasma activation, followed by a surface graft
polymerization.4-7 Composites are also formed to improve
adhesion.8,9 However, because of the much lower prize of wet
chemical treatments compared to composites or plasma ~vacuum!
processes, these treatments are preferred industrially. The adhesion
strength of a solid-solid interface is largely determined by the bond-
ing characteristics and structure of the interface.10 The work re-
quired to pull an interface apart consists of the work of adhesion
plus the work required to deform the two bulk materials. Increasing
the roughness of an interface increases the total amount of contact
surface between both materials and can increase both parts of the
work required to pull the interface apart. Hence, the influence of wet
chemical treatments on the evolution of polymer surface roughness
is important for the adhesion strength of plated metals on top of
polymers. The influence of industrial wet-chemical treatments on the
topography of the polymer surface and the changes at the interface
polymer-metal are described in a previous paper.11 A model is pre-
sented in Ref. 11 for the breakdown of the polymer chain at its
surface. This model implies certain mechanisms that cause the for-
mation of roughness on the surface of the polymer.
The conclusions of this paper are:
z
E-mail: sam.siau@elis.rug.ac.be
1. Etching with oxidizing agents of the polymer surface intro-
duces more polar groups at the surface.
2. Polar groups at the surface react with the oxidizing agent and
the difference in surface concentration leads to a difference in etch-
ing speed.
3. Usage of sweller agent increases the number of polar groups at
the surface. This causes an increase in the number of polymer break-
down groups.
These conclusions are based on time-independent measurements. In
this paper a kinetic verification of these conclusions is performed.
Distinction is needed between the phenomena associated with the
action of the sweller only and those which are a combination of the
actions of sweller and oxidizing agents. This requires knowledge of
the underlying mechanisms of reaction at the polymer interface with
the different chemicals used. Some of the mechanisms occurring
include: ~i! the sweller reorienting the polar groups at the surface;
~ii! the sweller moving through the free volume and causing swell-
ing of the polymer; ~iii! reaction of the oxidizer with groups at the
surface; ~iv! diffusion of the oxidizer agent to the surface of the
polymer for fast oxidation reactions; and ( v ) swelling with water,
the solvent of the oxidizing agent.
In this paper a quantitative description of the kinetics of the
sweller agent is given. Different models are proposed based on theo-
ries available in literature. Also a diffusion model is proposed for
sweller kinetics. Furthermore, a qualitative study of the influence of
the oxidizing agent on the roughness is given. This study will be
further developed in a next paper. The roughness of the samples is
measured by atomic force microscopy ~AFM!.
The development of roughness on the polymer surface is the main
contributor of the adhesion of electroless copper in the case of wet
processing.12-14
Studies of wet chemical treatments12,13 of epoxy surfaces re-
vealed an increase in the amounts of oxygen-containing functional-
ities on epoxy surfaces during the early stage of etching. The O/C
ratio at the surface of the polymer, as detected by X-ray photoelec-
tron spectroscopy ~XPS!, increases during a short ~smaller than 1
min! period of etching but remains constant after this initial in-
crease. With longer etching microcavities are formed and the rough-
ness becomes more pronounced.12 The failure mechanism of elec-
trochemically deposited copper on top of epoxy polymers is
cohesive in nature.11,12 This is the reason the surface roughness has
a big impact on the peel strength of electrochemically deposited
copper.11,12
Although these publications12-14 describe the influence of wet
 The remainder of this paper is not in-
cluded as this paper is copyrighted ma-
terial. If you wish to obtain an elec-
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an email to bib@elis.UGent.be with a
request for publication P104.051.pdf.