Development of Post-CMP Cleaners For Better Defect Performance

ECS Transactions, 44 (1) 565-571 (2012)
10.1149/1.3694370 The Electrochemical Society
Development of Post-CMP Cleaners for Better Defect Performance

Cuong Trana, Peng Zhanga, Laisheng Suna, Naresh Kumar Pentab, Uma Rames Krishna
Lagudub, Devon Shippb , S.V. Babub
a
ATMI, Inc USA
b
Clarkson University, USA
In the copper CMP process, organic residues that are related to
Benzotriazole (BTA) adsorbed on copper surface after Cu CMP
process have to be removed during the cleaning. In order to
address this organic defect issue, we present here the study of the
performance of BTA removal by post-CMP cleaners using copper
particles as substrates instead of copper wafers. In this work,
different copper particles including Cu(0), Cu(I) and Cu(II) oxide
particles with high surface area, were chosen to study the removal
of BTA adsorbed on different copper states. TGA and UV-Vis
spectra were used to detect and quantify the BTA removal
efficiency. The results by different post CMP cleaners on various
Cu particles will be presented.
Introduction
Post-CMP cleaners are used to remove various defects from the chemical mechanical
planarization (CMP) process. With the shrinking circuitry as the nodes advance to 20nm
and below, post-CMP cleaning faces greater challenge in improving cleaning
effectiveness and electrical performance. Continuous efforts have been made in
developing post-CMP cleaners with improved cleaning performance to remove particles,
metals and organic matters without damaging copper surface, as well as enabling superior
electrical performance.
Among various defects from CMP process, organic defects have been one of the major
challenges for post-CMP cleaning (1-2). In the copper CMP process, Benzotriazole
(BTA) is used in most slurries to provide the protection to the copper surface during
polishing. Copper ions can form a cuprous BTA complex (CuBTA) in the form of (3)
passivating films with multilayer polymeric structures (3). These BTA films and residues
are the main source of organic defects that have to be removed during the post CMP
cleaning step (1). Therefore, understanding the effect of post-CMP cleaning chemistries
on BTA removal is important for the development of next generation post-CMP products
with better defect performance.
Most prior studies of BTA adsorption and removal on copper surface are carried out on
copper wafers which have very small surface areas, leading to poor reproducibility and
non-conclusive results. In addition, the results were usually confounded by the presence
of both Cu(I) and Cu(II) oxides on copper wafer surfaces. In this paper, we developed the
method of using Cu(0), Cu(I) oxide and Cu(II) oxide particles to investigate the impact of
post-PCMP cleans on BTA removal.
Previously, Cu(I) oxide and Cu(II) oxide particles have been used to investigate the effect
of various components in slurries on the performance for chemical mechanical polishing
(4-6). By controlling the surface state of copper oxide, the mechanism of complexing
agents with amine and carboxyl function groups in slurries for copper CMP was
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elucidated (4). For the pCMP work, the large surface area and the controlled surface
states of these particles made them ideal candidates for quantitative investigation of BTA
adsorption and removal. In this paper, different copper particles including Cu(0), Cu(I)
and Cu(II) oxide particles were chosen , and TGA and UV-Vis spectra were used as
measurement for the BTA removal efficiency.
Experimental
Copper metal particles, Cu(I) oxide and Cu(II) oxide particles were purchased from
Alfa Aesar with purity of > 99% and used without any further treatment. These particles
were characterized by XRD to verify that their purity was suitable for next step
experiments.
The BTA adsorption on copper particles was carried out by dispersing 1% copper
particles in 10 mM BTA solution. The suspension was stirred for 1 hour to allow BTA to
fully adsorb on the surface of copper particles. After centrifuging, these particles were
washed thoroughly by water and centrifuged again to obtain BTA adsorbed copper
particles. Then the particles were transferred to diluted post-CMP formulation solutions.
The suspensions were stirred for certain time and then centrifuged. The supernatant
solutions were used for UV-Vis measurements. The copper particles were washed
thoroughly by water and then dried at 75oC overnight before the TGA measurements.
Commercially available post-CMP cleaner, PlanarCleanTM from ATMI, along with
other post-CMP formulations were used for evaluation of BTA removal from copper
particles. These pCMP cleaners were freshly prepared and diluted to certain ratios before
testing. DI water with different pH adjusted by KOH was also used for evaluation of pH
effect on the BTA removal from copper particles.
Results and Discussion
Characterization of Copper Particles
The SEM images of copper particles were shown in Figure 1. Copper metal
particles had round shape while Cu(I)O and Cu(II)O particles had irregular shapes. The
BET specific surface area and particle sizes of these copper particles were shown in
Table 1. The average size of copper metal particles was 1.6 m, smaller than those of
Cu(I)O and Cu(II)O particles. The specific surface area of copper metal particles was
0.69 m2/g. Compared to the surface area of a flat copper surface, 1 g of copper metal
particles has about the same surface area of a copper wafer with the surface area of 6900
cm2. This makes it much easier to use instrumental methods such as UV-Vis and TGA to
detect BTA adsorption and desorption from these particles.
Figure 1
SEM images of Cu metal particles, Cu(I)O particles and Cu(II)O particles

Table 1. BET specific surface area and particle size of copper metal and copper oxide
particles
Particles
Cu (-625 mesh)
Cu(II)O (-325 mesh)
Cu(I)O (-325 mesh)
Surface area (m2/g)**

0.69
0.17
0.53
Particle size (m)*

1.6
12.0
9.5
* Particle size measurements were conducted on Malvern Mastersizer 2000 instrument.

Copper and copper oxide particles were dispersed in water and sonicated to make
uniform suspensions.
** Specific surface area of copper particles was measured by the BET method.
TGA Study of BTA Removal from the Surface of Copper Particles
The adsorption of BTA molecules on copper surface with different oxidation
states was studied by the TGA method. Figure 2 showed the TGA curves of Cu metal,
Cu(I) oxide and Cu(II) oxide particles after BTA adsorption. For all copper particles, the
weight loss started from about 300oC, while pure BTA molecules started to lose weight at
about 150oC. This temperature difference could be attributed to the binding interaction of
BTA molecules on the surface of copper particles. The weight loss from the TGA curves
in Figure 2 could be used to estimate the amount of BTA adsorbed on copper particles.
Higher the weight loss in TGA curves, the more BTA molecules adsorbed on copper
surface. There was about 1.7% weight loss of BTA molecules adsorbed on Cu metal
particles, which is more than 1.0% on Cu(I) oxide and 0.4% on Cu(II) oxide particles.
Figure 2. TGA analysis of BTA adsorbed copper metal particles and copper oxide
particles.
These BTA adsorbed copper particles were subsequently used to evaluate the cleaning
performance of post CMP cleaners. The first step is to investigate the pH effect on BTA
removal using pH adjusted water with nitric acid or KOH. The cleaning efficiency based
on BTA weight loss was estimated from the following equation;

Cleaning Efficiency at x pH =
TGA wt loss at pH 4 - TGA wt loss at x pH

x100
TGA wt loss at pH4
Table 2 showed the cleaning efficiency of BTA from copper particles. It is clear that
BTA was barely removed from copper surface at pH below 8 regardless of the copper
surface states. When pH of water increased over 10, there was an obvious increase of the
BTA removal for all copper particles. When pH of water increased to 12, BTA cleaning
efficiency further increased significantly. This pH effect can be explained by the
deprotonation of BTA molecules which have a pKa of 8.2 at pH above 10.
Among all Cu particles, BTA molecules were more easily removed from Cu metal and
Cu(II) oxide particles than from Cu(I) oxide particles. In fact, at pH 12, most BTA
molecules were removed from Cu(II) oxide particles while much less BTA molecules
were removed from Cu(I) oxide particles. This is consistent with the previous report of
formation of multi-layer cuprous BTA complex on copper(I) surface (3). The cuprous
BTA complex layers cannot be removed with water by simply adjusting to higher pH.
Table 2: BTA removal from the surface of different copper particles by water with
different pH adjusted by KOH or HNO3
BTA cleaning efficiency %
pH of water
Cu
Cu(I)O
Cu(II)O
10
18
10
43
12
58
15
89
UV-Vis Spectra Study of BTA Removal from Copper Particles by PlanarClean

The second method of evaluating BTA removal was conducted via UV-Vis spectra of the
supernatant solutions. BTA solutions have distinct peaks around 270nm wavelength, as
shown in Figure 3. A linear calibration curve was obtained at pH 10, making it possible
for quantitative analysis of BTA concentration in the solution. Even though this method
does not directly probe the BTA concentration on copper surface, it is much more
convenient and faster than the TGA method. Therefore the majority of subsequent work
is conducted using this method.

a)
b)
Figure 3. a) UV-Vis spectra of BTA solutions at different concentrations at pH 10; b)
Calibration curve of BTA conc. at pH 10.
Figure 4. UV-Vis spectra of supernatants obtained from 60:1 PlanarCleanTM solutions

before and after treatment of BTA adsorbed copper(I) oxide particles. The inset is the
enlarged UV-Vis spectra showing the absorption between 400 nm and 800 nm.
TGA results from the previous section showed that it is difficult to remove BTA
molecules from the surface of Cu(I) oxide particles using pH effect alone. In the next set
of studies, formulated pCMP cleaners such as the commercially available post CMP
cleaner, PlanarCleanTM, were tested via UV-Vis method. Figure 4 showed the UV-Vis
spectra of the supernatant of 60:1 diluted PlanarCleanTM solutions after BTA removal
process. Diluted PlanarCleanTM itself showed some absorption at about 270 nm, and its
spectrum was subtracted from the sample signal. As shown in Figure 4, after BTA
removal, the absorption peak at 270 nm was very high, indicating the increase of BTA
concentration in the supernatant. This suggests that PlanarCleanTM was very effective in
removing BTA molecules from Cu(I) oxide surface. It is also noted that there was an
extra adsorption peak located at 600 nm, indicating a new form of Cu complex formed in
PlanarCleanTM solution during the BTA removal process (4).
Table 3 showed the UV-Vis absorption data of PlanarCleanTM solutions with different
dilution ratios after the treatment of BTA adsorbed copper particles. With dilution ratio

increased from 30 to 200, the absorbance at 270 nm decreased accordingly, indicating

that the efficiency of BTA removal from Cu(I) oxide particles decreased as the function
of dilution ratios. The absorbance at 600 nm also decreased with the increase of dilution
ratios.
Table 3 The absorption results of PlanarClean solutions with different dilution
ratios after treatment of BTA adsorbed Cu(I) oxide particles.
Dilution ratios
pH
UV Absorbance
of PlanarCleanTM
at 270 nm
at 600 nm
30:1
12.2
0.92
0.062
11.9
0.68
0.043
11.8
0.30
0.025
11.5
0.21
0.019
11.4
0.11
0.01
8
60:1
8
90:1
1
120:1
9
200:1
5
The new Cu complexes at 600nm wavelength seem to be a useful indicator of cleaning
from the surface of Cu(I) oxide particles. Figure 5 showed the absorbance comparison at
600 nm between three other post-CMP cleaners with PlanarCleanTM. The results showed
that the cleaner PC-C had the highest absorbance among all cleaners. It also had highest
absorbance at 270 nm indicating the highest BTA removal from copper surface. This is
consistent with the expected behavior of a new type of cleaning agent in PC-C
formulation. In addition, this trend is confirmed by the real tool evaluation data which
indicated that the PC-C formulation had the best cleaning performance among the
evaluated cleaners.
Figure 5. Comparison of copper complex formation in different PCMP formulations

Conclusions
Copper particles had higher surface area than copper wafers that are normally used in
study of BTA removal during post CMP cleaning process. Using copper metal, Cu(I)
oxide and Cu(II) oxide particles, BTA removal from copper surface could be analyzed by
TGA and UV-Vis spectra. The results showed that pH played a very important role in
BTA removal from copper particles, and higher pH favors the BTA removal efficiency.
Among different Cu states, BTA on Cu(I) oxide surface is more difficult to be removed
than from Cu(0) and Cu(II) oxide surfaces. Formulated cleans, such as PlanarCleanTM is
very effective in removing BTA from Cu(I) oxide surface. Further optimization with
new cleaning agents can enhance the BTA removal, as indicated by UV-Vis studies.
Acknowledgements
This paper is made possible through funding from ATMI for the collaboration project
between ATMI and Clarkson University. The authors acknowledge Jeff Barnes from
ATMI for various discussions.
References
1. Todd Buley, Yakov Epshteyn, Mike Kulus, Cuong Tran, Kyle Bartosh, Darryl
Peters, Chris Watts, in MICRO Magazine, Wet Surface Technologies,
October/November, 2005.
2. D. Peters, E. Walker, K. Bartosh, J. Barnes, C. Tran, and C. Watts, The 2nd
PacRim International Conference on Planarization CMP and its Application
Technology, pp. 68-72 (November 2005).
3. Desmond Tromans, J. Electrochem. Soc., 145, L42 (1998).
4. Venkata R.K. Gorantla, Dan Goia, Egon Matijevi and S.V. Babu, J. Electrochem.
Soc., 152, G912 (2005).
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ECS Transactions, 44 (1) 565-571 (2012)

10.1149/1.3694370 The Electrochemical Society