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Keywords:
BEOL cleaning
Post-etch residue removal
Deep eutectic solvent
Electrochemical impedance spectroscopy
a b s t r a c t
Eutectic mixture of choline chloride (CC) and malonic acid (MA) in a molar ratio of 1:1 has been evaluated
as a potential chemical system for the removal of residues produced by CF4/O2 plasma etching of copper
coated with DUV photoresist. Immersion cleaning was performed in the liquid at the eutectic composition at 40 and 70 C. Residue removal rate was screened using scanning electron microscopy and veried
using X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy measurements.
The results presented in this paper show that choline chloridemalonic acid eutectic is effective in
removing post-etch residues and has the potential to function as a back end of line cleaning formulation.
2011 Elsevier B.V. All rights reserved.
1. Introduction
New process challenges arise in the semiconductor industry as
device features scale down. In particular, post-etch residue removal in back end processes has become more challenging since
the introduction of copper interconnect structures. New materials
such as low-k and ultra-low-k (ULK) together with metal barriers
and copper lines add to the complexity of the residue material generated during patterning by gas phase etching. Finding cleaning
agents that are able to selectively remove these residues without
corroding Cu or affecting low-k critical dimensions is a challenge
in the semiconductor cleaning technology [1,2].
In BEOL processing, post-etch residues (PER) are formed during
plasma etching of low-k interlayer dielectric (ILD) layers using CF4,
CHF3 or C4F8 in combination with O2 or Ar to form the vias and
trenches for the different interconnection levels [3]. The plasma
etching also exposes the underlying copper (when the nitride etch
stop layer is removed) and leaves behind a polymer like residue on
Cu as well as on sidewalls of dielectric [4]. The residues typically
contain copper oxides, copper uorides, and uorocarbons among
others. Effective removal of PER is of critical importance in BEOL to
create good contact and adhesion between the deposited layers.
The efciency of residue removal is affected not only by the material complexity but also by where the residue is formed. Currently,
semi-aqueous uoride (SAF) cleaning formulations that contain
aprotic solvents, amines, uorides, water and in some cases, corrosion inhibitors are cleaning agents of choice in the semiconductor
industry [58]. However, the downside of these formulations is the
use of solvents that are not very environmentally friendly [9]. The
Corresponding author.
E-mail address: srini@u.arizona.edu (S. Raghavan).
0167-9317/$ - see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.mee.2011.11.014
Please cite this article in press as: J. Taubert et al., Microelectron. Eng. (2011), doi:10.1016/j.mee.2011.11.014
CC/MA was measured as a function of temperature using Brookeld DV-E viscometer equipped with a thermal cell. A sample volume of 7 mL was used and the spindle was rotated in the 5 and
100 rpm range, depending on temperature. Conductivity was measured with an Orion conductivity meter equipped with a temperature compensated Orion DuraProbe 4-Electrode conductivity cell.
300
250
Liquid
200
150
Eutectic point :
composition 1:1
temperature 10C
100
50
0
0
20
40
60
Malonic Acid [Mol %]
80
100
2. Experimental methods
2.1. Post-etch residue (PER) preparation
Electroplated copper lms of thickness 1.5 lm provided by an
integrated circuit company were pre-cleaned using isopropyl alcohol (Alfa Aesar, 99%) and 0.1 M hydrochloric acid (J.T. Baker, 96%).
DUV photoresist (TDUR-P802 HP, TOK America) lm of 500 nm in
thickness was spin coated on copper lm and then baked at 90 C
for 90 s. The lm was then plasma etched in a reactive ion etcher
(AGS) using CF4/O2 plasma chemistry (40 sccm CF4, 4 sccm O2), under 50 mTorr pressure and 250 W plasma power. Visually, the resist appeared to be etched at 3 min but the samples were
exposed for an additional minute to ensure complete resist removal. A pre-cleaned bare copper lm was exposed for 1 min to
the same plasma chemistry to serve as a baseline for copper samples exposed to plasma.
2.2. PER lm characterization
2500
3
Viscosity
2000
Conductivity
2.5
2
1500
1.5
1000
500
0.5
20
30
40
50
60
70
Conductivity [mS/cm]
Extent of removal of PER lms was evaluated by SEM and conrmed by XPS. Further verication was obtained from Electrochemical Impedance Spectroscopy (EIS) measurements based on
the method described previously [15,23]. The EIS experiments
were performed using PARSTAT 2273 (Princeton Applied Research). A three electrode set up was used with PER covered Cu
sample (or copper sample exposed to plasma) as the working electrode and platinum foils as quasi-reference electrode and counter
electrode. The area of the working electrode exposed to the liquid
was 1 cm2. An AC signal of 10 mV rms amplitude was applied and
the frequency was swept between 100 mHz and 100 kHz. The test
sequence was as follows. The sample was immersed in the DES system and at the end of 1 min of immersion, the impedance test was
started. It took approximately 90 s to cover the frequency range of
100 mHz to 100 kHz. Immersion was continued for 30 s and again
the impedance spectrum was taken. This process was repeated 2
more times. The data obtained are plotted as 2 and 1/2 min, 4
and 1/2 min, 6 and 1/2 min measurements. The data obtained were
tted to equivalent circuits using commercially available software
ZView (Scribner Associates) to extract the electrical parameters.
EIS analysis was not performed at 70 C due to the thermal instability of malonic acid in CC/MA DES. Malonic acid decomposition
is catalyzed by Pt (electrodes) at this temperature [24,25].
Viscosity [cP]
Temperature [C]
Fig. 2. Viscosity and conductivity of CC/MA liquid mixture as a function of
temperature.
Please cite this article in press as: J. Taubert et al., Microelectron. Eng. (2011), doi:10.1016/j.mee.2011.11.014
Fig. 3. SEM micrographs of (a) Cu exposed to CF4/O2 plasma for 1 min (Cu-1 m); (b) Cu-1 m cleaned for 5 min in CC/MA liquid at 40 C; (c) Cu-1 m cleaned for 5 min in CC/MA
at 70 C; (d) PER-lm formed after 4 min exposure to CF4/O2 plasma; (e) PER-lm cleaned for 5 min in CC/MA at 40 C; (f) PER-lm cleaned for 5 min in CC/MA at 70 C.
Please cite this article in press as: J. Taubert et al., Microelectron. Eng. (2011), doi:10.1016/j.mee.2011.11.014
Fig. 4. Comparison of Cu 2p, F 1s, O 1s and C 1s XPS spectra of PER-lm, copper exposed to plasma for 1 min (Cu-1 m), PER-lm cleaned for 5 min in CC/MA at 40 C and Cu1 m cleaned for 5 min in CC/MA at 40 C.
Fig. 5. Nyquist plots of Cu, Cu exposed to plasma and Cu coated with PER-lm in CC/MA at 40 C as a function of time.
the Cu 2p spectrum are those for elemental copper whereas shoulders at 952.5 and 932.5 eV are related to native oxides of Cu (+1)
formed during atmospheric exposure. The presence of Cu (+1) is
also conrmed by a peak at 529.9 eV in the O 1s spectrum. The
peak at 531.2 eV might be associated with C=O due to exposure
to contaminants from atmosphere [30]. For the C 1s spectrum, no
signicant change in the peak position was observed.
EIS measurements on PER lm coated Cu, plasma exposed Cu
and bare copper samples were made in CC/MA liquid at 40 C to
conrm residue removal. Impedance spectra were collected for
each sample as a function of time. Nyquist plots obtained from
the PER-lm coated Cu sample are shown as an example in
Fig. 5. In all the plots a depressed semi-circle is observed. This kind
of arc depression is usually due to surface inhomogeneities in the
electrode-material system [31]. A characteristic nite length War-
Fig. 6a. Randle circuit model with mass transport limitations to t impedance data
obtained on Cu sample immersed in CC/MA DES at 40 C.
Fig. 6b. Equivalent circuit model to t impedance data collected on PER-lm coated
Cu and Cu-1 m sample in CC/MA DES at 40 C.
Please cite this article in press as: J. Taubert et al., Microelectron. Eng. (2011), doi:10.1016/j.mee.2011.11.014
Table 1
Electrical parameters obtained by tting Nyquist plots of Cu, PER-lm and Cu exposed to plasma in CC/MA liquid mixture at 40 C as a function of time. Diffusion layer length L is
reported at the bottom of the table.
v2
L [lm]
Cu
PER-lm
2 and 1/2
530 6
29.5 2.0
0.80 0.01
758 154
1611 155
4.9 0.6
0.44 0.01
0.00042 0.00001
1.97
2 and 1/2
539 2
5.9 0.4
114 2
29.3 0.9
0.84 0.01
387 50
981 137
4.2 0.5
0.43 0.01
0.00029 0.00006
1.82
Cu-1 m
4 and 1/2
542 2
6.0 0.3
152 1
22.9 2.1
0.89 0.01
348 53
1494 123
6.3 0.2
0.45 0.01
0.00042 0.00002
2.24
Z W s R tanhjxTP =jxTP
where the parameter R corresponds to the Warburg element resistance related to the diffusion of the electroactive species.
The term
p
(jx) is the product of j, an imaginary number equal to 1, and x,
which is 2p times the linear frequency. The parameter T is related to
the length of the diffusion layer L and to the diffusion coefcient D
through the relationship, T = (L2/D), and P is an exponent related to
the slope of linear part in the Nyquist plot.
The impedance of constant phase elements, CPE, is dened as:
6 and 1/2
543 1
22.9 1.7
0.85 0.01
492 39
1952 91
8.5 0.5
0.44 0.0
0.0011 0.0003
2.61
2 and 1/2
531 47
5.6 0.7
137 4
31.9 2.7
0.81 0.03
462 44
1027 108
4.2 0.8
0.44 0.01
0.00027 0.00009
1.84
4 and 1/2
533 47
5.7 0.7
185 3
25.6 2.6
0.86 0.03
411 35
1548 78
6.6 0.8
0.44 0.01
0.00033 0.00005
2.29
6 and 1/2
531 47
24.3 0.9
0.83 0.01
615 57
1877 294
8.5 2.4
0.46 0.01
0.00076 0.00003
2.60
4. Conclusions
Liquid mixtures consisting of choline chloride (CC) and malonic
acid (MA) in a molar ratio of 1:1 were effective in removing residues formed by CF4/O2 plasma etching of copper coated with
DUV-photoresist. X-ray photoelectron spectroscopy (XPS) characterization showed that PER lm contains a mixture of copper uorides and copper oxides. The residues were effectively removed at
a rate of 30 min1 at 40 C.
Acknowledgements
The authors would like to acknowledge the nancial support
from SRC/Sematech Engineering Research Center for Environmentally Benign Manufacturing at The University of Arizona through
contract #2001-MC-424. The authors would like also to acknowledge fruitful discussions with Mr. Dinesh Thanu, whose previous
work on CC/U DES created the basis for this project.
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Please cite this article in press as: J. Taubert et al., Microelectron. Eng. (2011), doi:10.1016/j.mee.2011.11.014