Copper Post-CMP Brush Cleaning

Norbert Elbel*, Shumin Wang+,Annette Shger*, Dariusch Hadawi* and Chuck Held+
"Siemens AG, 81739 Munich, Germany, 'Cabot Corporation, Aurora, IL 60504
Abstract
Both metallic and abrasive particle cleaning after Cu CMP
process was studied. Two chemical, citric acid and K2-EDTA,
based cleaning systems were evaluated as functions of concentration and pH. Results of e 5 ' 10" at/cm2 for Cu contamination
were achieved with both optimized systems. Cu presented on
wafer surface in the form of homogeneous film, yet alumina was
detected in both localized particles as well as thin film. No Cu
corrosion nor surface roughening were detected after the cleaning
process.

Introduction
Copper has been accepted as the material of choice for subhalf micron interconnect technology. Due to the difficulties associated with RIE of copper, dual damascene and Cu CMP are most
commonly used to realize copper interconnects. One major challenge of copper wiring technology is to prevent copper from
diffusing into the active device regions (1). To meet this requirement, two conditions have to be fulfilled: (a) the copper lines
must be fully encapsulated by dense conductive and dielectric
barriers (2, 3), and (b) residual copper contamination, which is
usually present on the interlayer dielectric (ILD) surface after Cu
CMP, must be removed by an appropriate brush clean process (4).
In this paper, we demonstrate that the copper cleaning performance of a brush clean process can be enhanced by several
orders of magnitude by adding complexing agents to the cleaning
solution. The relationship between solution concentration, pH and
remaining copper contamination are experimentally studied by
total reflection X-ray fluorescence (TXRF) and vapour phase
decomposition (WD). Different surface analytical methods, such
as time-of-flight SIMS (TOF-SIMS), auger electron spectroscopy
(AES) and rutherford backscattering (RBS), are combined to
investigate, whether the residual metal contamination is mainly
present in form of particles or in form of a homogeneously distributed monolayer.

localized data points across the wafer were collected and averaged. This is to exclude the very edge of the wafer, where high Cu
residues were usually found (due to polishing process).

Results and Discussion

Preanalysis of contaminated ILD surface - Basically, CMP
induced metal contamination can be present on the ILD surface in
form of particles (e.g. abrasive particles) or in form of a homogeneous film (e.g. chemically dissolved then reprecipitated and
readsorbed on ILD surface). Since particle removal and metallic
film removal represent different cleaning issues, the detailed
knowledge of the physical and chemical appearance of metallic
contaminants is essential for the optimization of a post metal
CMP brush clean process. To clarify this point, oxide wafers,
contaminated by procedure (A) and subsequently brush cleaned
utilizing pure DI water, were analyzed by TOF-SIMS. Fig. 1
depicts TOF-SIMS images of a 20 x 20 pm2 surface region, which
contains a number of particles. The high Al signal in Fig. l a
indicates the particles to be mainly alumina from the abrasive. As
evident from Fig. 1b, the particles are partially coated with copper
due to Cu CMP processing.

Fig. 1: TOF-SIMS images (a: A1 signal, b Cu signal) of alumina abrasive

particles on oxide surface, which have been coated with Cu during CMF'
processing. Bright spots correspond to high signals, dark areas to low
signals. The average AI: Cu signal ratio is 100 : 5 . Image size is 20 x 20
pm2.

Experimental
All cleaning experiments were performed utilizing unpattemed 6" wafers. Prior to brush cleaning, the wafers were contaminated with copper by one of the following procedures:
(A) Blanket oxide wafers were polished for 30 sec inbetween
blanket copper wafers.
(B) Blanket copper wafers were polished just to clear.
All the polishing was carried out with Cabot Cu slurry. The contaminated wafers were brush cleaned with OnTrak double side
scrubber using different cleaning solutions. Metallic contamination of the wafers from process (A) was analyzed utilizing VPDAAS, which integrates the entire wafer surface. Wafers contaminated with process (B) were characterized by TXRF, of which 9

0-7803-5174-6/99/$10.000 1999 IEEE

Fig. 2: TOF-SMS images (a: AI signal, b: Cu signal) after enlarging the

scan range to 75 x 75 pm2. The "windowing" is due to AI and Cu desorption during consecutiveimaging of the initial scan region (see Fig. 1).

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In Fig. 2, the TOF-SIMS scan range has been enlarged to 75 x 75

pm2. The previous scan region can be easily identified by the
lacking AI and Cu background signal in Figs. 2a and 2b, respectively. This "windowing" is due to the desorption of a thin AI/Cu
film during consecutive imaging of the initial 20 x 20 pm2 region.
Fig. 2 thus indicates that both, AI and Cu are not only present in
form of particles, but also in form of a homogeneos film.

ble, water-soluble copper complexes. To deprotonate the organic

acids, the pH of the cleaning solution was adjusted to 9.5 by
KOH. According to Fig. 4, at a pH of 9.5 CA and EDTA are
dissociated at 100%and at 15%, respectively.

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To further specify the above results, integrating measurement

techniques (VPD-AAS) and extremely surface-sensitive techniques (RBS, AES) were employed to quantify the Cu and Al
contamination. While VPD is expected to detect particles as well
as thin film contamination, AES and RBS reveal an information
depth of only about 3 nm and are thus insensitive to macroscopic
particles. The experimental results are summarized in Fig. 3. As
far as Cu contamination is concerned, VPD and RBS yield nearly
identical results. This indicates that Cu is almost exclusively
present in form of a homogeneous film. On the contrary, the Al
concentration measured by VPD differs by one order of magnitude from the corresponding AES measurement result. From this
we conclude that, roughly, 90% of the Al contamination is due to
alumina particles from the abrasive and 10% is due to a thin
adsorbed Al film.

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Fig. 3: Comparison of VPD, RBS and AES with respect to Cu and AI

detection. Ihe VPD signal originates from the entire oxide layer, whereas
the information depth of RBS and AES is only about 3 nm.

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Fig. 4: Calculated portion of completely dissociated citric acid (dashed

line) and K2-EDTA (continuous line) as a function of pH.

Copper cleaning - The challenge of Cu cleaning is to reduce

the contamination on the ILD surface to a level e 5 . 10" at/cm2
without causing corrosion to the damascene copper structures. To
meet this requirement, moderately reactive complexing agents
were added to the cleaning solution. In the present study, citric
acid (CA) and the potassium salt of ethylene-diamine-tetra-acetic
acid (K2-EDTA) were used. Both agents are known to form sta-

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Distance from wafer center [mm]

Fig. 5: Comparison of pure DI water, EDTA and citric acid with respect
to Cu cleaning performance. The wafers were contaminated by procedure
(B) and analyzed by %point TXRF measurements.

In Figs. 5a and 5b, the cleaning performance of pure DI

water is compared to the cleaning performance of CA and EDTA
at different concentrations. In case of the DI water clean, a Cu
contamination level of = 5 . lOI3 at/cm2 (corresponding to about
5% of a Cu monolayer) is detected. This level can be reduced by
more than three orders of magnitude, i.e. to values below 5 . 10"
at/cm2, by adding 1% EDTA or 1% CA to the cleaning solution.
Lower concentrations yield in higher Cu contamination. In comparison to CA, the cleaning performance of EDTA reveals a more
pronounced concentration dependence, which is supposed to be
due to the lower dissociation rate of only 15%. In Fig. 5, the
wafer center appears to be cleaned more efficiently, whereas the
wafer edge requires higher solution concentrations to be cleaned
to the same low Cu level. This result is attributed to the fact that
the OnTrak brushes (through which the cleaning solution is delivered) are in permanent contact with the wafer center, but not
with the wafer edge. The VPD data depicted in Fig. 6 correspond
well to the TXRF analysis shown in Fig. 5. Again, the EDTA
clean reveals a more pronounced concentration dependence than
the CA clean. One way to improve the edge cleaning is to increase
the brushing time.
In addition to contamination removal, corrosion control is
an important challenge of post CMP brush cleaning. To investigate to what extend the Cu surface is chemically attacked by the
cleaning solution, Cu sheet film wafers were polished for 1 min
(but not cleared) and subsequently brush cleaned with 1% EDTA
and 1% CA, respectively. From 4-point film thickness measurements prior to and post brush cleaning, the dynamic wet etch rates
of both chemicals were determined to be below 5 nmlmin. As
revealed by AFM 'measurements, the investigated cleaning solu-

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tions do not cause any corrosion or surface roughening. Hence,

EDTA as well as CA can be considered to be appropriate additives for effective copper brush cleaning.

EDTA

Citric acid

particles is to remove a thin oxide layer by an HF brush clean.

However, the use of HF might be critical with respect to copper
corrosion, and the enviromental concern of fluoride has always
been an issue. Another strategy is to generally reduce the defectivity level by optimizing the Cu CMP consumables, such as the
pads, and the polishing process, such as down force, platen speed,
pad conditioning. In addition, a buffing step on a soft pad can
help to minimize particles associated with CMP defects.

Fig. 6: Cu cleaning performance of EDTA and citric acid at different

concentrations. The wafers were contaminated by procedure (A) and
analyzed by VPD-AAS.

Alumina particle cleaning - As discussed above, A1 is

present on the ILD surface mainly in form of alumina particles
from the abrasive. Since alumina can hardly be dissolved by
complexing agents, the particles have to be cleaned off mechanically. To increase the efficiency of particle removal, the zeta
potentials of abrasive, wafer surface and brush material in the
cleaning solution should be considered. The isoelectric points of
S O z , A1203and PVA can be found at pH values 3, 8.5 and 2,
respectively (5). By choosing a pH above 8.5 all materials involved in the system have like charge, so no electrostatic adhesion
can occur. Therefore the pH dependence of alumina particle
removal was investigated too.

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Fig. 8: AFM image and line profile analysis of alumina particles, which
are partially embedded into the oxide surface.The dashed line in the AFM
image indicates the line profile trace.

Conclusion
In conclusion, we have shown that brush cleaning with
EDTA as well as with CA is effective in removing Cu contamination from the ILD surface. At solution concentrations of 1% the
Cu contamination level is reduced to values below 5 ' 10" at/cmz.
As revealed by AFM measurements, the investigated cleaning
solutions are not corrosive to the Cu damascene structures.
If alumina particles are partially embedded into the oxide
surface, they will be difficult to be removed by conventional
brush cleaning. HF brush cleaning and optimized CMP
consumables and the process as well as a CMP buffing step are
feasable strategies to reduce the overall surface defectivity.

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Acknowledgements

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The authors wish to thank Chris Baker, Vlasta Brusic and

Colin Schmidt at Cabot for wafer polishing and Cu corrosion
measurements and Chris Yu for managerial supervise.

PH

Fig. 7: AI contamination after EDTA cleaning at 0.1% solution concentration and at pHs from 6.0 to 11.5. The pH was adjusted by KOH. Contamination procedure (A) and VPD-AAS have been used.

Oxide wafers were contaminated by procedure (A) and

subsequently brush cleaned with 0.1% EDTA at pHs from 6.0to
11.5. As can be seen from the VPD data shown in Fig. 7, within
the investigated pH range the AI concentration is measured to be
constant at a considerably high level of -- 2 . lOI4 at/cmz. This
result can be understood from an AFM analysis of the polished
oxide surface. Fig. 8 depicts an AFM image of a linear sequence
of surface indentations as possibly generated by agglomerated
particles during CMP processing. As can be seen from the line
profile on the right hand side of Fig. 8, the indentations are partially filled with (alumina) particles. Since the particles are embedded into the oxide layer, they are difficult to be removed by
brush cleaning. One effective way to clean off embedded alumina

References
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