Journal of The Electrochemical Society, 161 (5) D207-D213 (2014)

D207

An Electrochemical Method of Suppressor Screening for Cu

Plating in Sub-100 nm Lines
Q. Huang,,z J. Liu, and B. Baker-ONeal
IBM T. J. Watson Research Center, Yorktown Heights, New York 10598, USA
A two-step transient method was developed to electrochemically screen suppressor molecules toward the applications in Cu plating
chemistry for narrow trenches. The first potential transient with full amount of suppressor was acquired to simulate the potential
applied on the wafer, which is largely determined by the plating of the field region on the wafer. A second current transient experiment
with the potential controlled by the transients acquired in the first experiment is used to mimic the plating at different locations across
the wafer. When different fractional amounts of suppressor are injected into the second experiment, the current transients acquired
thereof simulate the plating rate in the trench structure. A slower super filling rate at higher plating current was well predicted by the
transient method and was confirmed by filling experiments. A good qualitative correlation was also observed between the current
transients and the filling performance of different suppressors.
The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/),
which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in
any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. [DOI: 10.1149/2.015405jes]
All rights reserved.
Manuscript submitted January 16, 2014; revised manuscript received February 20, 2014. Published March 7, 2014. This was Paper
1932 presented at the Boston, Massachusetts, Meeting of the Society, October 914, 2011.

Cu electroplating has been one of the critical steps in the Cu interconnect technology, which has been used for over a decade in
semiconductor and microelectronic devices.1,2 The Cu electroplating
is a so called super-conformal filling or super filling process, where
the deposition rate at the bottom of a structure is much faster than
the rate at the top of the structure so that the structure is filled void
free. These super filling processes generally rely on the organic additives in the plating solution, particularly, the suppressor and accelerator. The additive behavior318 and the associated properties of the
plated Cu films1925 have been extensively studied. As the dimensions
of the state-of-the-art semiconductor devices scale, advanced plating
chemistries are demanded to form the structures defect free.
The mechanism of the super conformal filling has been studied
extensively. A widely adopted mechanism was proposed by Moffat
et al.912 and West et al.,13 where an accumulation and crowding of the
accelerator was proposed to occur on the Cu surface at the bottom of
the structure due to a continuous shrinkage of the Cu growth front surface area during plating. This so-called curvature enhanced accelerator
coverage (CEAC) hypothesis is in agreement with the observations
that the accelerator floats on top of the Cu surface during plating11
and that the plating rate suppressed by the suppressor is promoted
by the accelerator due to a displacement or disruption of the surface
passivation film.12 The CEAC model therefore successfully explains
a faster local plating rate at the bottom of the feature, resulting in the
super filling. The CEAC mechanism also predicts a bump formation
on top of dense patterns of small structures due to the locally high
surface coverage of accelerator after the structures are filled.10,13 In
addition, the CEAC mechanism predicts that a pre-treatment of the
Cu substrate in a more concentrated accelerator solution can provide
a higher initial coverage of accelerator. Therefore, the curvature enhancement of the accelerator coverage can be achieved, facilitating
the super filling, in a plating solution with suppressor only.11
Another widely used model was put forward by Akolkar and
Landau16,26 to address the transient effect of the suppressor. Due
to the fast adsorption and slow transport of suppressor molecules
such as PEG, the fast transport of accelerator molecule, SPS, and
the slow displacement of suppressor by accelerator, they predicted
a suppressor concentration gradient along the feature depth, which
is established immediately after the substrate is immersed into the
electrolyte. This concentration gradient of the suppressors, coupled
with the interaction with accelerator, was used to explain the faster
Cu plating at the bottom of the structure. Although a concentration

Electrochemical Society Active Member.

E-mail: qhuang@us.ibm.com

gradient is typically involved in the leveling mechanism in a plating

solution, this is a new perspective of looking at the suppressor
behavior in the super filling mechanism.
The impact of the diffusion and distribution of suppressor was
demonstrated by Akolkar and Dubin, where they observed a much
slower filling rate on the isolated structures compared with the nested
structures.27 They further simulated the suppressor distribution and
correlated the slower filling rate of the isolated structure with a thinner
depletion zone of the suppressor. Another observation of the importance of the suppressor concentration gradient to the super filling is
presented in Figures 1. Three substrates with 80 nm wide lines were
plated in the same Cu plating solution with different diffusion conditions. Super conformal and defect free filling was observed for the
sample plated with hot entry, where the plating starts as soon as the
substrate is immersed in the solution. On the other hand, conformal
plating was observed when sonication was used during the plating or
when a time delay was applied between the immersion and the plating. While the sonication promotes the mass transport of suppressor,
a time delay allows more time for suppressor to diffuse into the narrow features. The suppressor concentration gradient is believed to be
mitigated in both cases and therefore resulted in conformal plating.
As the interconnects keep scaling the sub-100 nm trenches are
filled within a short period of plating time, generally within 5 seconds.
Therefore, suppressors that quickly establish a suppressing state and a
big contrast between the plating rates at top and bottom of the trenches
are in demand. While an ultimate correlation between the suppressor
molecular structure and its filling performance is not available and is
difficult to establish at this point, electrochemical screening methods
are needed to identify the promising suppressor candidates. In a previous paper, we developed a screening method using potential transients
(galvanostatic plating) with injection of the full amount of accelerator and different partial amounts of suppressor.28 Potential transient in
presence of full amounts of both accelerator and suppressor represents
the plating situation at the opening of a trench. Due to the presence
of a suppressor concentration gradient, the plating at different depth
of the trench was experimentally simulated by the transients with full
amount of accelerator and different fractions of the full amount of suppressor. The difference between the potential transients with full and
partial doses of suppressor was used to evaluate the difference in the
suppression of the plating between the top and the bottom of the trench.
While a large difference between the potential transients with partial and full doses of suppressor was correlated to a better filling
performance, the potential transients do not provide direct information on the super filling rates. A larger difference in the potential does
not always guarantee a larger difference in the current, i.e. the plating

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Journal of The Electrochemical Society, 161 (5) D207-D213 (2014)

Figure 1. Cross sectional SEM images of 80 nm wide lines after 6 second plating with (a) hot entry, (b) hot entry and sonication during plating,
(c) 1 second delay of the plating current after immersing the substrate into the
solution.

rate. The later also depends on the polarization behavior of the chemistry. In this paper, we further developed a quasi-potentiostatic plating
method for suppressor screening. This method is to better electrochemically simulate the real plating of the patterned substrates and
to provide a more direct comparison of the filling rates for different
suppressors and for different plating conditions.
Experimental
An AUTOLAB potentiostat-galvanostat electrochemical system
was used for the study. Cu plating was carried out using an electrolyte
containing 0.63 M CuSO4 , 0.1 M H2 SO4 and 1.5 mM HCl. Different
experimental versions of the CUPUR suppressors from BASF SE
were used for suppressor screening development and filling tests. In
these studies, the different suppressors were compared at a fixed,
vendor recommended dose. The concentration of the accelerator, bis(sodium sulfopropyl)-disulfide or SPS, was kept constant. Two other
commercial additive packages, Chemistry A and C, were used in the
study as well with the vendor-recommended doses.
Chronopotentiometry (potential transients) and chronoamperometry (current transients) were acquired to electrochemically characterize the additives. A typical three-compartment cell with a glass frit to
separate the anode and cathode was used. Pt mesh was used as the anode in the anode compartment. A saturated mercury sulfate electrode
(MSE) was used as the reference. A Pt rotating disk electrode (RDE)
was used at 100 rpm as the cathode. The Pt RDE was pre-plated at
20 mA/cm2 for 10 second in the additive-free virgin make-up solution (VMS) before each transient characterization. During a typical
transient study, 50 mL VMS premixed with the calculated amount of
additives was added into 150 mL VMS, where a magnetic stirrer was
used for mixing. In this paper, the different amounts of suppressors
are referred to with respect to the recommended dose. For exmple,
1 and 1/5 refer to one portion of and one fifty of recommended
dose, respectively.
Filling experiments were performed on 2 cm 2 cm patterned
chips with 20 nm PVD Cu seed. The structures of interest are nested
trenches, around 40 nm wide and 140 nm deep. The post-liner-seed
aspect ratio of the different trenches varied from 3 to 5. Chips were
plated with constant current without agitation. Hot entry was used and
the time of the plating was controlled with an electronic timer-switch.

Figure 2. (a) Typical potential transients at galvanostatic plating with the

injection of full dose of accelerator and (green solid line)1, (red dash line)
1/5, (purple dash dot line) 1/20, and (black long dash line) 1/100 of the
full dose of suppressor. (b) Zoom in potential transients with illustrations of
data extraction from the curves.

The galvanostat was turned on before the sample being immersed,

and the electrochemical system was at overload mode. As soon as
the sample was being immersed, the potential dropped to the value
corresponding to the applied plating current and the timer started ticking. The circuit was opened (switched off) once the plating time was
up. This electronic switch allowed an accurate control of the plating
time with hot entry. The chips were then cleaved perpendicular to the
trenches and coated with a carbon-based ink. The cleaved samples
were polished with a focused ion beam (FIB) after a portion of the
cleaved edge being protected with Pt (in the FIB tool). After polishing, the prepared samples were imaged with a scanning electron
microscope (SEM) at the cross section.
Results and Discussion
As discussed in the introduction, a potential transient method with
the injection of full amount of accelerator and different fractions of
the full amount of suppressor was developed previously to simulate
the different additive adsorption rates across the depth of the trench.28
Figure 2 shows the typical potential transient curves and the method
of data extraction from the curves. Upon the injection of the additives in galvanostatic plating, the potential shifts negatively due to the
fast adsorption of suppressors onto the Cu surface. A positive shift
of the potential follows afterwards as the accelerator displaces the
suppressor. The potential response suggests how suppressed or how
accelerated the plating is at any moment when there is a fractional
amount of suppressors. Since a suppressor concentration gradient is
present across the depth of the trench, the difference between these
potential curves simulates the suppression of the plating at different
locations across the depth of trenches.

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Journal of The Electrochemical Society, 161 (5) D207-D213 (2014)

As illustrated by Figure 2b, at t after the injection, the plating potential at the location where 1 of suppressor is present in the solution
is higher, by E1 , than the location where only 1/5 of suppressor is
present. This potential difference is E2 between the locations where
1/5 and 1/20 of suppressor are available. A shielding coefficient
was introduced to describe the ratio of the suppressor adsorption onto
the sidewall and onto the bottom of the trenches. This shielding coefficient tells the equivalent fraction of the suppressor that is available at
bottom of the trenches in terms of the suppressor adsorption rate. It can
be calculated with numerical simulation or estimated with an approximate equation.28 For trenches with aspect ratio of 3.5, the equivalent
suppressor concentration at the bottom of the trench is about 1/20 of
the concentration at the top of the trench. Therefore, the larger E1
and E2 are, the more difference is between the plating at the top and
at the bottom of the trenches. However, this difference is actually the
potential difference between the top and the bottom of the trench if
they were plated at the same current.
In the real plating process, the whole wafer, including the trenches
as well, is plated with a continuous Cu seed. Therefore the different
locations along the depth of a trench are plated at a same potential.
While there might be a potential difference across the whole wafer
when the Cu seed layer is extremely thin or when more resistive seed
materials are used, the potential difference across the trench depth is
negligible. At a same potential, the bottom and the top of the trench
are plated at different rates as a result from the different additive
adsorption behaviors at these different locations. For a state-of-the-art
interconnect wafer, structures with different dimensions are present
and are plated at the same time. The sub-100 nm features are a small
portion of the total wafer area. Therefore, once the wafer is immersed
into the solution, the plating potential is determined by the plating
behavior of the so-called field region, or the blanket area, and the
top of the trenches. This plating potential at the field region changes
along the time and this potential profile depends on the adsorption
and desorption of the additives on the Cu surface. The plating at the
bottom of the trenches is controlled by this potential profile. But it
also depends on the additive diffusion and adsorption behavior at
the bottom of the trench. Therefore, a current transient measurement
controlled by that potential profile with the injection of different doses
of the additives is believed to better simulate the plating scenario at
the different depths of a trench.
A suppressor screening method was therefore developed consisting
of two types of transient experiments. A first experiment was carried
out to acquire the potential transient when the full doses of accelerator
and suppressor were injected. This potential transient represents the
plating potential for the top of the trench and the field region or the
whole wafer. The second plating experiment was controlled by this
potential transient profile. A full dose of accelerator and a fractional
dose of the suppressor were injected together at the same time when
the additives were injected in the first experiment. Figure 3 shows
the experimental results for the commercial Chemistry C, including a
potential transient from the first experiment and the current transients
from the second experiment. The additives were injected at t = 50
sec in all experiments, to simulate a wafer plating with the wafer
immersed into the solution at t = 50 sec.
In Figure 3, a constant current density of 3 mA/cm2 was used in
the first experiment. The curve (a) is the potential transient with the
injection of 1 suppressor and 1 accelerator at t = 50 sec. Curve (b)
is the potential used in the second experiment to acquire the current
transients. In the real practice, the AUTOLAB was operated in the
so called sweep-and-hold mode. The curve (b) is a segmented linear
approximation of the potential profile of curve (a). While the digitalto-analog converted signals would simulate the true potential profile
more accurately, the linear approximation is believed to simulate the
profile well enough for the studies. A small leading time of 1 sec was
purposely added to the curve (b) as compared to the original potential
profile, curve (a). In addition, different partial doses of suppressor and
full dose of accelerator were injected at t = 50.2 sec (instead of 50 sec)
during the second experiment. The total delay of 1.2 sec of the additive
injection with respective to the potential profile is to avoid the chance

D209

Figure 3. (a) Potential transients acquired during the galvanostatic plating

experiments with the injection of full doses of accelerator and suppressor;
(b) Potential profile applied in the current transient experiments; (c-h) The
current transients acquired with the plating controlled by the potential profile:
(c) without any additive injection and (d-h) with the injection of 1 accelerator
and (d) 1, (e) 1/4, (f) 1/10, (g) 1/20, (h) 1/100 suppressor.

where the additives in the second experiment are added too early due
to experimental variation, which will introduce a current dip in the
transients. While having additives at the bottom of the trench earlier
than at the top is against reality, this 1.2 sec delay is expected to create
a small over-estimation in the difference between the plating rates at
the bottom and the top of the trenches. Curves (c) and (d) are two
current transients acquired with two different additive concentrations
with the plating controlled with the potential profile (b).
Curve (c) was acquired in the VMS without adding any additives,
representing the highest possible current density that can be achieved
at the bottom of the trench, where no suppressor is available. While
an injection of accelerator alone would be a more accurate representation, its difference from curve (c) was negligible (not shown). Curve
(d) is the current transient with the injection of 1 suppressor and
1 accelerator at t = 50 sec. This curve represents the lowest current
density that can be possibly achieved at the bottom of the trench, where
the suppressor diffuses fast or the trench is shallow and the suppressor
concentration is the same as the bulk. It is evident that the current
density in curve (d) stays constant at about 3 mA/cm2 except for an
initial current spike. The spike lasted for about 3 seconds and is related
to the 1.2-sec leading time of the potential profile (b) with respect to
the injection of the additives in the second experiment. However, this
short-lasting current spike suggests that the aforementioned 1.2-sec
delay in the additive does not affect the current transients beyond a
few seconds. In addition, the constant current observed after the spike
at about 3 mA/cm2 , the same as the current density used in the first
experiment, further validates the experiments. This constant current

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Journal of The Electrochemical Society, 161 (5) D207-D213 (2014)

is a result of the mutual annihilation of the effects of two processes.

Firstly, the applied potential shifts negatively at t = 50 sec (ignore
the 1.2 sec difference) and then changes according to the pre-acquired
potential profile. Secondly, the additive adsorbs and/or desorbs at Cu
surface, starting at the same t = 50 sec (ignore the 1.2 sec difference).
From the first experiment, the potential applied here is the potential
required to maintain the constant current density of 3 mA/cm2 when
1 suppressor and 1 accelerator are injected at t = 50 sec. As long as
the applied potential profile and the additive behavior at the Cu surface
are synchronized in the second experiment, these two effects cancel
each other and the current in curve (d) maintains at 3 mA/cm2 . In
other words, if the suppressor and accelerator concentrations at the
bottom of the trench were the same as at the top of the trench, the
plating rates at these two locations would have been the same and
stays constant.
Current transient curves (e) to (h) represent the different intermediate cases between (c) and (d), where different fractional amounts of
suppressor are injected. As discussed above, a concentration gradient
of suppressor is established due to the slow diffusion and fast adsorption of suppressor. Due to the small opening and high aspect ratio of
the trenches, forced convection is believed to be minimal inside the
trenches. While numerical simulation of the suppressor diffusion and
adsorption can be used to calculate the suppressor concentration at
any point, a simplified equation was previously developed to estimate
the equivalent suppressor concentration at the bottom of a trench.28
For a typical trench structure in the state-of-the-art interconnects, the
post liner-seed aspect ratio is about 3 to 6. The estimated equivalent
suppressor concentration at the bottom of the trench is between 1/17
to 1/40 of the bulk concentration. For a trench structure with nonideal etch profile and/or PVD liner-seed profile, this ratio can be even
bigger. Fractional doses of 1/4 to 1/100 of the recommended dose of
suppressor were used in the second experiment.
When 1/4 suppressor was injected, the current transient is similar
to the case where 1 was injected, current approximately stays at
constant after a short current spike at the beginning. However, when
1/10 or less suppressor was injected, the current further increases
beyond the time range of the spike. This current increase is due to
a much slower suppressing film formation on the Cu surface at a
much lower suppressor concentration. In detail, the suppressors start
to adsorb at the bottom of the trench, resulting in a suppressed state of
plating. However, the suppressing effect at the top of the trench builds
up much faster. The potential change overwhelms the formation of the
suppressing film at the bottom of the trench and therefore the current
continues to increase. As the suppression effect at the top of the
trench saturates the potential stops increasing anymore. Furthermore,
due to the presence of the accelerator, the potential starts to shift
positively after the saturation. On the other hand, the suppression
effect at the bottom of the trench builds up much more slowly and
does not saturate until much later. Therefore in a longer term, the
suppression effect formation at the trench bottom dominates and a
current decrease was observed, confirmed by Figure 3. A peak current
was therefore observed, indicating the maximum possible plating rate
at the bottom of the trench.
The super filling ratio is defined as the ratio of the plating rate at the
trench bottom over the rate at the trench top. In the current transient
studies in Figure 3, the plating rate at trench top is the current that
was applied during the potential transient experiment, 3 mA/cm2 .
In an effort of comparing the super filling performance at different
current densities, three sets of experiments were carried out at three
different plating current densities. Each set of experiments includes a
potential transient at the applied current density, and a series of current
transients for each of the acquired potential profiles.
Figures 4a 4c show the current transients normalized with the
plating current densities of 3, 5, and 10 mA/cm2 . Only three
fractional injections of suppressor, 1/4 , 1/20 , and 1/100 are
presented. Assuming an aspect ratio of 3.5 for the trench structures,
the equivalent suppressor dilution at the trench bottom is 1/20. The
maximum super filling ratios were about 10, 6.4, and 3.2 for the three
current densities used. In other words, the ratio between the plating

Figure 4. (a-c) Normalized current transients acquired during the second experiment, where the (d) potential profile was acquired with a galvanostatic
plating at (a, d1) 3, (b, d2) 5, (c, d3) 10 mA/cm2 . The suppressor dose
fractions are (dashed line) 1/4, (solid line) 1/20, and (long dashed line) 1/100.

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Journal of The Electrochemical Society, 161 (5) D207-D213 (2014)

Figure 5. Cross sectional SEM images of 40 nm wide trenches plated at

(a) 3, (b) 5, (c) 10 mA/cm2 for (a) 3.4, (b) 2, (c) 1 sec.

D211

rate at the trench bottom and the plating rate at the top is
much higher at a lower plating current density. Figure 5 shows the
cross sectional SEM images of 40 nm wide trenches plated at 3,
5, and 10 mA/cm2 . While the total charge of plating was the
same for the three cases, the trench was filled much faster at the
lower current density. This observation on the 40 nm wide trenches
confirms the prediction from the current transients in Figure 4. Due
to the super filling in the trenches, the average current density on
a patterned substrate is higher than the current density in the field
region, or at the top of the trenches. Therefore the observation in
Figure 5 is a qualitative rather than a quantitative confirmation of the
super filling ratio observed in Figure 4.
An interesting observation in the transient curves is that the peak
currents were about the same across the three studies in spite of
the different applied potentials, shown in Figure 4d. The potential
difference between 3 and 5 mA/cm2 remains at a constant of
about 50 mV. This 50 mV resulted in a small difference between the
peak current in the current transients, 30 and 32 mA/cm2 , corresponding to a super filling ratio of 10, and 6.4. On the other hand,
while the potential difference between 5 and 10 mA/cm2 is also
about 50 mV in VMS, the difference is smaller after the injection of
the additives. When the current transient is concerned, the effect of
this smaller potential difference was even further diminished. Both

Figure 6. Normalized current transients in the second experiments and the filling performance for five different suppressors, (i) to (v), at a plating current density
of 3 mA/cm2 . The 40 nm wide trenches were plated for 3.4 sec. The suppressor dose fractions are (dashed line) 1/4, (solid line) 1/20, and (long dashed line)
1/100.
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Journal of The Electrochemical Society, 161 (5) D207-D213 (2014)

potential profiles resulted in a peak current of 32 mA/cm2 , corresponding to the super filling ratio of 6.4 and 3.2.
As the interconnect structure continues to scale, the thickness of
the liner and Cu seed decreases, too. The dissolution of the Cu seed,
especially the air-oxidized Cu seed, becomes more of a concern in the
plating. In addition, the thinner Cu seed demands a good nucleation
on a possibly partially exposed liner material.29 In general, a higher
bias or a higher current density is beneficial for nucleation and seed
protection. Therefore, a plating chemistry that enables a good super
filling at a high current density is in demand. The transient method
described above provides a screening method to compare or even
predict the filling performance on trenches of different aspect ratios
at different current densities. This method can be further extended to
structures of non-ideal geometries as well.
Figure 6 shows the normalized current transients and the filling
performance for five different experimental versions of BASF CUPUR
suppressors. A plating current of 3 mA/cm2 was used for both the
screening transients and the filling experiments. It is evident from
the SEM images that the suppressors (ii) and (iv) resulted in a much
more conformal filling, or a much lower super filling ratio. Among
the other three, the suppressor (v) completely filled the trench and (iii)
almost filled the trench with a very nice bottom up growth profile.
While suppressor (i) also showed nice super filling ratio as compared
with (ii) and (iv), some trench to trench variation was observed on
the super filling ratio. All the current transients of these different
suppressors showed a maximum super filling ratio from 8 to 10,
similar to chemistry C in Figure 4. However, the suppressors differ
drastically in how long that peak current lasts in the transient study. All
the three suppressors that provide a good filling performance, (i) (iii)
and (v), showed a much longer peak current than the two suppressors
that dont, (ii) and (iv). The filling experiment was carried out on
trenches with straighter side walls and aspect ratio of 5, of which
the equivalent dilution factor for suppressor is 1/35. Although this
difference in the duration of the peak current is less obvious for 1/20
dilution cases, it is much more pronounced for 1/100 dilution.
Figure 7 shows the normalized current transients and the cross
sectional SEM images of plated trenches for two other chemistries,
Chemistry A and C, at a higher current density of 5 mA/cm2 .
Figure 7a is a replot of Figure 4b. Different peak currents and different
durations of the peak current were observed for the two chemistries.
With 1/100 suppressor injection, Chemistry C reached a super filling
rate of 6.4 while chemistry A only reached 5.5. With 1/20 suppressor, this difference becomes even bigger, 6.3 vs. 3.1. In addition, the
peak current of Chemistry A lasts much shorter than Chemistry C.
These differences are believed to result in the much slower super filling or much more conformal plating for Chemistry A as observed in
the SEM images.
While the above results demonstrated a method to screen different
suppressors, the method is rather qualitative. One main concern of this
method is that the transient study spans for more than 100 seconds
while the trenches are filled within 5 seconds in real practice. Ideally,
in order to accurately characterize the chemistry within a few seconds
of plating, the transient experiments described here need to be carried
out with the premixed plating solutions to avoid the mixing effect
and with electronic trigger to avoid the current spike (discussed in
Figure 3). More quantitative comparison and more accurate suppressor screening are expected by using the hot-entry transients into the
premixed solutions. The method described in this paper uses transients
in a longer time scale, which yet reflect the nature of the suppressors
and qualitatively correlate to the behaviors of the suppressors at a
shorter time scale. The method is believed to be one of the many
steps toward an ultimate method to electrochemically characterize
and predict the super filling performance of additives.
Another concern of the screening method described here might
be the absence of the leveler. In a real wafer plating process, a third
additive, leveler, is generally used to mitigate the surface topography
created by the momentum plating, a result of super filling.3032 It is
desired and designed in most commercial chemistry packages that
the leveler is neither absent inside the trenches at all or exerts little

Figure 7. Normalized current transients in the second experiments and the

filling performance for (a,c) Chemistry C, and (b,d) Chemistry A at a plating
current density of 5 mA/cm2 . The 40 nm wide trenches were plated for 2
sec. The suppressor dose fractions are (dashed line) 1/4, (solid line) 1/20, and
(long dashed line) 1/100.

impact to the behavior of the suppressor and accelerator inside the

trenches in real practice. The second possible way of changing the
super filling by the leveler is that the presence of leveler in the bulk
solution can change the potential bias applied to the wafer, or the
potential transients acquired during the first experiment.33 However,
this leveler effect is only present in a longer time scale, typically after
about 20 seconds,33 as compared with the filling time, typically within
5 seconds. The potential response within a few seconds is independent
of the presence of leveler and is only determined by the suppressor
and accelerator. Therefore, the transient experiments in this paper
were carried out without leveler for the screening of suppressors with
regards to their filling performance.
Finally, the transient method discussed above is not able test the
CEAC behavior. In other words, it does not provide information on
how the suppressors influence the accelerator coverage change in
response to the Cu surface area shrinkage. Figure 8 shows the normalized current transients in an attempt to characterize the accelerator

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Journal of The Electrochemical Society, 161 (5) D207-D213 (2014)

D213

the IBM T.J. Watson Research Center and the IBM Albany Nanotech
Center are greatly appreciated for providing the substrates for the
study. BASF SE is also acknowledged for supplying the experimental
suppressor molecules.
References

Figure 8. Normalized current transients in the second experiments for Chemistry C at a plating current density of 3 mA/cm2 and with the injection of (a)
1/4 (b) 1/20 suppressor and (a1, b1) 1, (a2, b2) 2, and (a3, b3) 5 of
acceelrator.

concentration effect. In this study, multiplied doses of the accelerator

were injected together with fractional doses of suppressor. No effect of
the accelerator concentration was observed on either the peak current
height or the duration. While the accelerator coverage is expected to
change as the Cu surface curvature evolves during plating, this effect
on the surface adsorption could not be easily simulated by having more
accelerators in the solution. As the surface shrinkage during the super
filling of the vias is more pronounced than the filling of the trenches,
the CEAC effect is expected to be stronger during the filling of the
vias. However, the method described in this paper is believed to be extendable for the filling of the vias as a qualitative screening method for
the suppressor molecules. The suppressor concentration gradient in a
via can be simulated or computed in a similar way as for trenches.28
Conclusions
In an effort to electrochemically identify suppressor molecules
for good super filling performance, a two-step transient method was
developed as an improvement from the previous potential transient
method.28 A potential transient during galvanostatic plating with full
amount of suppressor was acquired firstly to simulate the potential
applied on the wafer during the plating, which is largely determined by
the plating of the field region on the wafer. While this potential is not a
constant, it is used to control the second plating experiment to mimic
the plating at different locations across the wafer. Due to the slow
diffusion and fast adsorption of suppressor, a concentration gradient is
present across the depth of the trenches. Therefore, different fractional
amounts of suppressor are injected into the second experiment to
simulate plating inside the trench structure. The current transients
acquired thereof reflect the plating rates across the depth of the trench.
A lower super filling ratio at higher plating current density predicted
by the transient method was well confirmed by filling experiments.
A good correlation was also observed between the current transients
and the filling performance for different suppressor molecules. While
this correlation is still qualitative, hot entry transient experiments with
improved control is expected to allow more quantitative comparison
of the suppressors.
Acknowledgment
Dr. Alexander Fluegel at BASF SE is acknowledged for helpful
discussions. The Nano Science and Technology Laboratory (NSTL) at

1. P. Andricacos, C. Uzoh, J. Dukovic, J. Horkans, and H. Deligianni, IBM Journal of

Research and Development, 42(5), 567 (1998).
2. D. Edelstein, J. Heidenreich, R. Goldblatt, W. Cote, C. Uzoh, N. Lustig, P. Roper,
T. McDevitt, W. Motsiff, and A. Simon, presented at the International Electron
Devices Meeting, IEDM, 1997.
3. J. P. Healy, D. Pletcher, and M. Goodenough, Journal of Electroanalytical Chemistry,
338(1), 155 (1992).
4. J. P. Healy, D. Pletcher, and M. Goodenough, Journal of Electroanalytical Chemistry,
338(12), 167 (1992).
5. J. P. Healy, D. Pletcher, and M. Goodenough, Journal of Electroanalytical Chemistry,
338(12), 179 (1992).
6. J. Kelly and A. West, Journal of The Electrochemical Society, 145, 3472
(1998).
7. J. Kelly and A. West, Journal of The Electrochemical Society, 145, 3477 (1998).
8. J. Kelly, C. Tian, and A. West, Journal of The Electrochemical Society, 146, 2540
(1999).
9. T. P. Moffat, D. Wheeler, W. H. Huber, and D. Josell, Electrochemical and Solid-State
Letters, 4, C26 (2001).
10. T. P. Moffat, J. E. Bonevich, W. H. Huber, A. Stanishevsky, D. R. Kelly,
G. R. Stafford, and D. Josell, Journal of The Electrochemical Society, 147, 4524
(2000).
11. T. Moffat, D. Wheeler, M. Edelstein, and D. Josell, IBM Journal of Research and
Development, 49(1), 19 (2005).
12. T. Moffat, D. Wheeler, and D. Josell, Journal of The Electrochemical Society, 151,
C262 (2004).
13. A. C. West, S. Mayer, and J. Reid, Electrochemical and Solid-State Letters, 4, C50
(2001).
14. M. Hayase, M. Taketani, K. Aizawa, T. Hatsuzawa, and K. Hayabusa, Electrochemical
and Solid-State Letters, 5, C98 (2002).
15. K. C. Lin, J. M. Shieh, S. C. Chang, B. T. Dai, C. F. Chen, and M. S. Feng, Journal
of Vacuum Science and Technology B: Microelectronics and Nanometer Structures,
20(3), 940 (2002).
16. R. Akolkar and U. Landau, Journal of The Electrochemical Society, 151, C702
(2004).
17. P. Vereecken, R. Binstead, H. Deligianni, and P. Andricacos, IBM Journal of Research
and Development, 49(1), 3 (2005).
18. J. W. Gallaway, M. J. Willey, and A. C. West, Journal of The Electrochemical Society,
156(8), D287 (2009).
19. T. Ritzdorf, L. Graham, S. Jin, C. Mu, and D. Fraser, presented at the Proceedings of
the IEEE 1998 International Interconnect Technology Conference, 1998.
20. J. M. E. Harper, C. Cabral, P. C. Andricacos, L. Gignac, I. C. Noyan, K. P. Rodbell,
and C. K. Hu, Journal of applied physics, 86(5), 2516 (1999).
21. K. Ueno, T. Ritzdorf, and S. Grace, Journal of applied physics, 86(9), 4930 (1999).
22. S. Lagrange, S. H. Brongersma, M. Judelewicz, A. Saerens, I. Vervoort, E. Richard,
R. Palmans, and K. Maex, Microelectronic Engineering, 50(1), 449 (2000).
23. S. C. Chang, J. M. Shieh, B. T. Dai, M. S. Feng, and Y. H. Li, Journal of The Electrochemical Society, 149(9), G535 (2002).
24. S. H. Brongersma, E. Kerr, I. Vervoort, A. Saerens, and K. Maex, Journal of materials
research, 17(3), 582 (2002).
25. M. Willey and A. West, Journal of The Electrochemical Society, 153, C728 (2006).
26. R. Akolkar and U. Landau, Journal of The Electrochemical Society, 156, D351
(2009).
27. R. Akolkar and V. Dubin, Electrochemical and Solid-State Letters, 10, D55
(2007).
28. Q. Huang, B. C. Baker-ONeal, J. J. Kelly, P. Broekmann, A. Wirth, C. Emnet,
M. Martin, M. Hahn, A. Wagner, and D. Mayer, Electrochemical and Solid-State
Letters, 12(4), D27 (2009).
29. J. Kelly, X. Lin, T. Nogami, O. van der Straten, J. Demarest, J. Li, R. Murphy,
X. Zhang, C. Penny, and C. Parks, Journal of The Electrochemical Society, 160(12),
D3171 (2013).
30. S. Kim, D. Josell, and T. Moffat, Journal of The Electrochemical Society, 153, C826
(2006).
31. T. P. Moffat, D. Wheeler, S. K. Kim, and D. Josell, Journal of The Electrochemical
Society, 153, C127 (2006).
32. J. D. Reid and J. Zhou, presented at the 209th ECS Meeting - International Symposium
on Electrochemical Processing in ULSI and MEMS 2, Denver, CO, 2007.
33. Q. Huang, B. C. Baker-ONeal, C. Parks, M. Hopstaken, A. Fluegel, C. Emnet,
M. Arnold, and D. Mayer, Journal of The Electrochemical Society, 159(9), D526
(2012).

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