Microelectronic Engineering 55 (2001) 383388

www.elsevier.nl / locate / mee

Advanced silver-based metallization patterning for ULSI

applications
T.L. Alford*, Phucanh Nguyen, Yuxiao Zeng, J.W. Mayer
Department of Chemical, Bio, Materials Engineering, NSF Center for Low Power Electronics, Arizona State University,
Tempe, AZ 85287 -6006, USA
Abstract
Silver metallization is being investigated for potential use in future integrated circuits. Unlike the proposed copper
metallization, Ag thin films can be reactive ion etched at reasonable rates using a CF 4 plasma. This etch technology is an
atypical dry-etch process since the formation of volatile products is not the main removal mechanism. The primary film
removal mechanism, however, is the subsequent resist strip process. The effects of process conditions on the etch rate and
post-etch surface roughness is also characterized. Our study shows that the silver etch process in the CF 4 plasma depends
strongly on the reactive neutrals and the removal rate is enhanced significantly by the presence of energetic ions as well.
2001 Elsevier Science B.V. All rights reserved.
Keywords: Silver-based metallization; ULSI applications; Integrated circuits; Etching processes

1. Introduction
To fulfill the desire of ever increasing device speed, advanced interconnect materials continue to be
one of the crucial factors to reduce the resistancecapacitance (RC) delay times. Silver has the lowest
room-temperature bulk resistivity [1] and is believed to have higher electromigration resistance than
that of Al. Based on these reasons Ag is considered to be one of a potential metallization schemes for
future integrated circuits (IC). However a pattern transfer technology is needed to enable the
integration of Ag into conventional semiconductor fabrication operations. This necessitates that the
processes be compatible with the current equipment and processes in modern IC fabrication facilities.
Halogen admixtures with oxygen, and oxygen glow discharges have shown potential as reactive
species to pattern silver [24]. The ultimate goal is to elucidate the mechanisms and parameters that
meets the stringent IC pattern-transfer requirements (i.e., high removal rate, high selectivity, post-etch
surface smoothness, corrosion elimination, and good edge geometries).
In this study, a pure CF 4 plasma process of silver is investigated. The issue of post-etch corrosion,
*Corresponding author. Tel.: 1 1-480-965-7471; fax: 1 1-480-965-3534.
E-mail address: alford@asu.edu (T.L. Alford).
0167-9317 / 01 / $ see front matter
PII: S0167-9317( 00 )00471-8

2001 Elsevier Science B.V. All rights reserved.

384

T.L. Alford et al. / Microelectronic Engineering 55 (2001) 383 388

edge geometry, and removal rates are also investigated. Our newly developed CF 4 -based patterning
technique is unique because it utilizes a plasma process and a wet chemical clean to obtain
anisotropically etched lines.

2. Experiment
Silver films were deposited onto a SiO 2 layer using an electron-beam-evaporation technique. Both
Ag and oxide layers were typically on the order of 200 nm. Optical lithography techniques were
employed to transfer the pattern to the wafer. The photoresist was then developed using a commercial
developer. The samples were then etched in a single wafer reactor. A 13.56-MHz generator and
matching network provided the RF power. The CF 4 gas entered from the top plate and through a
diffuser to produce a uniform flow distribution in the chamber. In order to investigate the effect of
process conditions on the Ag removal in a CF 4 plasma, experiments consisting of a full two-level
factorial design with three factors (pressure, power, and CF 4 flow rate) and two center-point replicates
is conducted [5].
The reacted films generated by exposure to the plasma processes and resist were removed in warm
(808C) photoresist-strip solvent. SEM analysis was employed to examine the post-plasma-exposed
and post-clean surfaces. Etch profiles were measured using a surface profiler with a stylus diameter of
12.5 mm. Due to the large diameter of the tip, all the measurements were taken between the large
300-mm square pads. The separation between pads was nominally 200 mm. Rutherford backscattering
spectrometry (RBS) was employed to analyze the post-clean samples. X-ray photoelectric spectroscopy (XPS) was also used to analyze the surface chemistry of blanket samples.

3. Results and discussion

Results from the blanket samples etched in pure CF 4 at 100 W and 100 mTorr provides information
about the surface constitutes. Fig. 1 shows the SEM micrograph for the as-etched and the post-clean
samples (i.e., after a solvent clean in warm photoresist strip). XPS measurement results of these
samples are listed in Table 1. The data indicates that the constituents of the as-etched surface are
carbon and oxygen (approximately of 89% atomic concentration). Silver, silicon, and fluorine
represent trace amounts of 2.1, 2.9, and 6.0 (percent atomic concentration), accordingly. This verifies
that a portion of the Ag had been removed because Si signal is detected and it is believed to come
from the underlying SiO 2 layer. The results also show that a post clean in warm solvent (808C) further
enhances of the removal of the reaction product. This is evident by the reduction in the Ag atomic
concentration to an amount ( , 0.3% atomic concentration) and the complete removal of fluorine. The
carbon concentration decreases during this process, while both the oxygen and silicon concentrations
increase.
Removal rates were studied as a function of power in the range of 50200 W, at constant pressure
of 100 mTorr for various CF 4 flow rates (20, 25, 30, and 40 sccm). This assisted to discern the effect
of power on removal rate and to confirm the insignificant effect of flow rate. At low powers, the etch
rate was low (see Fig. 2). Once the initiation power was reached, the etch rate increased rapidly with
power. The removal rate did not depend on the inlet gas flow rate for the range investigated here.

T.L. Alford et al. / Microelectronic Engineering 55 (2001) 383 388

385

Fig. 1. SEM micrographs of (a) as-etched and (b) post-clean samples etched in a CF 4 plasma (30 sccm, 100 mTorr, 100 W,
45 s). The post-clean sample confirms the removal of Ag. There is, however, some residue remaining on the SiO 2 substrate.

Higher power resulted in higher energetic ions that induced sputtering of surface materials. This
increased the reactive surface area and resulted in an increased fluorination rate. Ions therefore had to
gain sufficient energy (typically a few hundred electron-volts [6,7]) to overcome typical surface
binding energies for surface material to be sputtered. In this study, sputtering started to occur at about
100 W. Removal rate appeared to scale linearly as a function of power in the range of 100175 W.
To further demonstrate the effect of power on the removal rates, RBS is employed to analyze
post-clean blanket samples after exposure to CF 4 plasmas of 50 and 100 W. Fig. 3 shows the RBS
spectra of the above two samples and the as-deposited sample. For better illustration, etched samples
signals are increased by factors of 5 and 50. Inspection of Fig. 3 reveals that the Ag is completely
removed in the sample etched at 100 W; whereas, portions of the Ag are still present on the surface
for the sample etched at 50 W. The lower concentration indicates that the surface Ag is not pure and
the sloping back edge is due to the surface roughness [8].
Table 1
Atomic and mass concentrations as obtained from XPS analysis for as-etched and post-clean samples a
Samples

Element

Atomic %

As-etch

Si 2p
C 1s
Ag 3d
O 1s
F 1s

2.86
54.79
2.07
34.27
6

Post-clean

Si 2p
C 1s
Ag 3d
O 1s

11.91
32.26
0.33
55.51

The etch was done in a CF 4 glow discharge.

386

T.L. Alford et al. / Microelectronic Engineering 55 (2001) 383 388

Fig. 2. A plot of removal rates a function of power. This illustrates the insignificant effect of flow rate on removal rates.

Fig. 3. RBS spectra of post-cleaned samples etched at different powers in a CF 4 plasma (30 sccm, 100 mTorr, and 50 s).
The spectrum of the sample exposed to 50 W shows some Ag present on the surface; whereas, there is no Ag present on the
sample exposed to 100 W. For better illustrations, the signals of etched samples at 50 and 100 W are increased by factors of
5 and 50 times, respectively.

T.L. Alford et al. / Microelectronic Engineering 55 (2001) 383 388

387

Fig. 4. A plot of removal rates dependence on pressure. The plot displays a maximum removal rate at 150 mTorr for 100 W,
and 20 sccm.

Fig. 4 shows the removal rate as a function of pressure. In this plot the removal rate versus pressure
curve is concave down with a maximum at about 150 mTorr. This is indicative for the range of
pressure in this study (25200 mTorr). The removal rates are small at low pressures where the
reactive neutral flux arrival to the surface is low. This confirms that the removal rate has a strong
chemical dependence. As the pressure increases up to 150 mTorr, the neutral species-flux arrival at the
surface increases and a higher removal rates is observed. This suggests that neutral species play a
significant role in the surface reaction with Ag. As the pressure increases above 150 mTorr, the
neutral species fluxes arrival to the surface increases and results in higher removal rates. This results
in more collisions occurring in the bulk plasma and enhances recombination of reactive radicals at the
surface. This results in a decrease in the etch rate. These findings support the premise that the removal
mechanism of Ag in a CF 4 discharge depends on reactive neutrals and that the surface reaction is
transport limited. As an example (Fig. 5), the pattern etch of Ag is clean and uniform for the process
conditions: 30 sccm, 100 mTorr, 100 W, and 90 s.

4. Conclusions
In this study, we have developed a novel technique to pattern Ag using a CF 4 plasma followed by a
resist strip in warm solvent. The subsequent solvent clean also removes the reacted Ag materials
formed during the plasma exposure. The removal rates depend strongly on power. Inlet flow rates

388

T.L. Alford et al. / Microelectronic Engineering 55 (2001) 383 388

Fig. 5. SEM micrograph of Ag metal lines and pads after a CF 4 etch (30 sccm, 100 mTorr, 100 W, 90 s). This micrograph
displays a clean and uniform surface.

show insignificant effect. Evidence of sputter-assisted etching is seen clearly in the power effect study.
When the power reaches 100 W, the removal rate starts to increase significantly with power. The
surface reaction is mostly chemical with a strong enhancement by sputtering. With the ability to
pattern Ag using this technique, the post etch corrosion, removal rates, and resist erosion issues are
improved. This is a very important step toward the integration of Ag metallization into interconnect
technology.
Acknowledgements
The work was partially supported by The National Science Foundation, NSF (L. Hess, Grant No.
DMR-9624493) to whom the authors are greatly indebted. Support for the Center for Low Power
Electronics is provided by NSF, The State of Arizona, Analog Devices, Analogy, Burr Brown,
Hughes Aircraft, Intel, Microchip, Motorola, National Semiconductor, Rockwell, Scientific Monitoring, Texas Instruments, and Western Design.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

D.R. Lide (Ed.), CRC Handbook of Chemistry and Physics, 72nd Edition, Chemical Rubber, 1991.
P. Nguyen, Y. Zeng, T.L. Alford, J. Vac. Sci. Technol. B 17 (5) (1999) 2204.
M.K. Bhan, P.K. Nag, G.P. Miller, J.C. Gregory, J. Vac. Sci. Technol. A 12 (1994) 699.
C.H. Chou, J. Phillips, J. Vac. Sci. Technol. A 9 (1991) 2727.
Design-Expert Version 5. Stat-Ease Corporation, Minneapolis, 1996.
D.M. Manos, D.L. Flamm, in: Plasma Etching: An Introduction, Academic Press, Cambridge, 1989.
M.A. Lieberman, A.J. Lichtenberg, in: Principles of Plasma Discharges and Materials Processing, Wiley, New York,
1994.
[8] L.C. Feldman, J.W. Mayer, in: Fundamentals of Surface and Thin Film Analysis, North-Holland, New York, 1986.