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Abs. 604, 204th Meeting, © 2003 The Electrochemical Society, Inc.

Detection of Accelerator Breakdown Products in Copper

Plating Baths
M. Pavlov, E. Shalyt, P. Bratin and D. M. Tench
ECI Technology, Inc.
1 Madison Street, East Rutherford, NJ 07073

Acid copper sulfate baths are employed in the 6

Ar (mC)
"Damascene" process1 to electrodeposit Cu within fine trenches 2.0 ppm MPS
and vias in dielectric material on semiconductor chips. Two
organic additives are required to provide bottom-up filling of the 1.0 ppm MPS
Damascene features. The "suppressor" additive, which is 0.5 ppm MPS
typically high-molecular-weight (MW) polyethylene glycol 2 1.0 ppm SPS
(PEG), adsorbs strongly on the Cu cathode surface, in the VF
presence of chloride ion, to form a film that sharply increases
the overpotential for Cu deposition. The "anti-suppressor" or 0
“accelerator” additive counters the suppressive effect of the 0 2 4 6 8 10 12 14 16
suppressor to provide the accelerated deposition within trenches CVS Cycle Number
and vias needed for bottom up filling. Fig. 1 Plot of Ar as a function of CVS cycle number for acid
Close organic additive control needed for Damascene copper supporting electrolyte containing SPS,
plating is provided by Cyclic Voltammetric Stripping (CVS) Viaform™ or Ultrafill™ additives, and various
analysis, which involves alternate plating and stripping of Cu at concentrations of MPS.
a Pt rotating disk electrode. The additives are detected from the
effect that they exert on the electrodeposition rate measured via
the Cu stripping peak area (Ar). The accelerator concentration is 10
typically determined by the linear approximation technique MPS Concentration
(LAT) or modified linear approximation technique (MLAT).2 2.0 ppm
During Damascene Cu plating, however, the accelerator species 8
breaks down into species that may interfere with the
electrodeposition process. These accelerator breakdown 1.0 ppm
products must also be controlled if high quality Damascene 6
A (mC)

deposits are to be consistently obtained.

0.5 ppm

This paper describes a CVS method for detecting the

mercaptopropanesulfonic acid (MPS) breakdown product of the
0.25 ppm
bis(sodiumsulfopropyl)disulfide (SPS) additive that is widely
used for Damascene copper plating. The method involves 2
measurements of Ar on consecutive CVS cycles to detect the
time-dependent effect of MPS in suppressing the copper
deposition rate. 0
CVS measurements were made using a Qualilab QL- 0 0.2 0.4 0.6 0.8 1
10® plating bath analyzer (ECI Technology, Inc.). The Log (CVS Cycle Number)
supporting electrolyte contained 157 g/L CuSO4 . 5 H2O, 10 g/L
H2SO4, and 50 ppm chloride ion. The potential of the Pt rotating
disk electrode (2500 rpm) was scanned at 100 mV/s between a Fig. 2 Plot of Ar vs. Log (cycle number) as a function of
positive limit of +1.575 V and a negative limit of -0.225 V vs. MPS concentration.
SSCE-M. During CVS measurements, the solution temperature
was controlled at 25°C within +0.5°C. The effects of the 1
commercial Viaform™ (Enthone Inc.) and Ultrafill™ (Shipley,
Slope of A vs. Log Cycle Number

Inc.) additives (at normal concentrations) were investigated.

Figure 1 shows that Ar is constant for acid copper
baths containing SPS, Viaform or Ultrafill additives but
decreases monotonically with potential cycling in the presence -1
of the MPS breakdown product. The MPS species apparently
accumulates irreversibly on the Pt electrode surface and -2
suppresses Cu deposition.
Figure 2 shows that the decrease in Ar produced by

MPS is exponential since a plot of Ar vs. Log (cycle number) is
linear. As indicated by the standard curve shown in Fig. 3, the
slope of such plots provides a measure of the MPS -4
References: 0 0.5 1 1.5 2
1. P. C. Andricacos, Electrochem. Soc. Interface, p. 32, Spring MPS Concentration (ppm)
2. R. Gluzman, Proc. 70th Am. Electroplaters Soc. Tech. Conf.,
Sur/Fin, Indianapolis, IN (June 1983) Fig. 3 Dependence of slope of Fig. 2 plots on MPS