Spin-on Cu films for ultralarge scale integrated metallization

Hirohiko Murakami, Masaaki Hirakawa, Yoshiro Ohtsuka, Hiroyuki Yamakawa, Nobuya Imazeki, Shigeo Hayashi
, Toshihiro Suzuki, Masaaki Oda, and Chikara Hayashi

Citation: Journal of Vacuum Science & Technology B 17, 2321 (1999); doi: 10.1116/1.590911
View online: http://dx.doi.org/10.1116/1.590911
View Table of Contents: http://scitation.aip.org/content/avs/journal/jvstb/17/5?ver=pdfcov
Published by the AVS: Science & Technology of Materials, Interfaces, and Processing

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 Spin-on Cu films for ultralarge scale integrated metallization
Hirohiko Murakami,a) Masaaki Hirakawa, Yoshiro Ohtsuka, and Hiroyuki Yamakawa
Tukuba Institute for Super Materials, ULVAC JAPAN, Ltd., Tsukuba, Ibaraki 300-2635, Japan
Nobuya Imazeki, Shigeo Hayashi, Toshihiro Suzuki, Masaaki Oda, and Chikara Hayashi
Nanoparticle Division, Vacuum Metallurgical Co., Ltd., Sanbu-cho, Sanbu-gun, Chiba 289-12, Japan
共Received 15 March 1999; accepted 2 July 1999兲
We have developed the spin-on Cu metal 共SOM兲 process to fill trenches and vias down to 0.3 ␮m.
SOM is a liquid material that contains an organic solvent and dispersed ultrafine particles as a
source of Cu. This solution was applied to a Si wafer using a spin coater to form a film. Coated
wafers were baked at 623–673 K for 10 min in a reducing atmosphere. The end result is a Cu film.
Contrary to the conventional deposition techniques, the SOM process is simple but advantageous to
its gap filling, planarization, and cost consideration. © 1999 American Vacuum Society.
关S0734-211X共99兲05405-0兴

I. INTRODUCTION filling and planarization. As the name implies, SOM is a

liquid containing an organic solvent and dispersed ultrafine
Cu has been studied widely as an interconnection material
particles as the Cu source. For details on dispersed ultrafine
during the 1990s, for aluminum alloys which have been used
particles, refer to our former articles.4,5
in semiconductor devices, which so far have caused func-
Figure 1 shows the process flow to fabricate Cu films
tionality and reliability problems. Cu is thought to be the
using SOM process: 共a兲 SOM was applied to a Si wafer
most attractive substitute for aluminum alloys in ultralarge-
using a spin coater at a speed adjusted to form a film about
scale integrated circuits 共ULSIs兲 due to its lower resistivity
300 nm thick per coat. 共b兲 Next, the coated wafer was preb-
and better electromigration resistance.1 To use Cu as an in-
aked in first-stage heat treatment on a hotplate for 1 min at
terconnection material, pattern definition must be easy, but
573 K. 共c兲 Last, curing was conducted at 673 K for 10 min in
the dry etching of Cu is known to be difficult.2 The dama-
a reducing atmosphere. The end result is a Cu film. For thick
scene process is expected to be the solution for the patterning
layers, two or three coats may be required. Here, a Ti layer
of copper. In this process, metal patterns are fabricated by
was sputter deposited as a glue and a TiN layer as a barrier
filling preformed patterns with metal and chemical mechani-
on a patterned wafer.
cal polishing of the excess metal on the upper surface of
A spin-on Cu seed layer 200 nm thick was deposited for
preformed patterns.3 So, this process poses an entirely differ-
electroplating. A 1.5 ␮m thick Cu film was deposited by
ent set of requirements for Cu films. Dry etching, for ex-
electroplating using a commercially available plating bath
ample, would not be required, since Cu metal would be de-
consisting of sulfuric acid, Cu sulfate, and hydrochloric acid,
posited in the patterned film. Thus, the damascene process
along with the recommended amount of organic additives.
requires advanced properties in filling a high-aspect gap and
Sheet resistance of spin-on Cu films was measured using
a highly flat topology.
a four-point probe. A cross section of Cu-filled trenches was
Spin-on glass technology has been used in dielectric ap-
analyzed by scanning electron microscopy 共SEM兲 to evaluate
plications mainly due to its good gap filling and planarization
SOM filling. Adhesion strength of the spin-on Cu film was
combined with relatively low cost. This means that spin-on
tested in a tape-peeling test, i.e., the surface of the sample
technology is potentially applicable to the damascene pro-
was divided into 1⫻1 mm square pieces by scratching lines
cess, if Cu film can be deposited. In this article, we propose
with a diamond stylus, then Scotch tape was applied to the
a new spin-on technique, i.e., spin-on Cu metal that uses
scratched surface, and rapidly peeled off. The Cu film texture
ultrafine Cu particles to enhance Cu deposition at the bottom
was measured using an x-ray technique. Impurities in
of trenches and vias at 673 K and possibly even lower tem-
spin-on Cu film were analyzed by secondary ion mass spec-
peratures. Step coverage exceeding 100% enables defect-free
troscopy 共SIMS兲 and Auger electron spectroscopy.
filling of sub-0.5 ␮m features such as 0.3 ␮m wide trenches
and 0.3 ␮m vias having a high aspect ratio. We then dem-
onstrate spin-on Cu seed applicability to electrochemical
deposition 共ECD兲 Cu. III. RESULTS AND DISCUSSION
A transmission electron microscope 共TEM兲 image of the
SOM 共Fig. 2兲 shows Cu particles well separated from each
II. EXPERIMENT
other because of surfactants covering particle surfaces. The
Unlike conventional deposition techniques, the spin-on average Cu particle size is about 8 nm and the particle size
Cu metal 共SOM兲 process is simple and provides good gap distribution is very sharp. SOM viscosity, which is a very
important factor for the liquid process, was adjusted to 2
a兲
Electronic mail: hmurakam@ulvac.trc-net.co.jp ⫻10⫺3 Pa s for spin coating. Cu concentration, which is an-

2321 J. Vac. Sci. Technol. B 17„5…, Sep/Oct 1999 0734-211X/99/17„5…/2321/4/$15.00 ©1999 American Vacuum Society 2321

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 2322 Murakami et al.: Spin-on Cu films for ULSI metallization 2322

FIG. 3. Spin-on Cu gapfill and planarization mechanism.

FIG. 1. Spin-on Cu film formation process flow.

other key parameter for the SOM process, was adjusted to 10 ness, so this provides step coverage exceeding 100%. This
and 20 wt % for seed layer and gap fill processes, respec- enhanced copper deposition at the bottom of trenches leads
tively. to complete planarization of metallized structures. 共This is
One of the most important reasons for using the SOM illustrated in Fig. 3.兲 Filling of trenches was observed from
process to fabricate inlaid conductors for ULSI devices is its the bottom of trenches 共Fig. 4兲, primarily because surface
superb gap filling. A SOM solution spun onto a wafer mi- tension of the liquid pulls the film flat—a self-planarization
grates down into deep features, enhancing filling and reduc-
ing void formation better than low-mobility sputter deposi-
tion. The SOM process does not require two general
techniques developed to enhance gap filling in sputter depo-
sition process: reflow, based on high temperature, and the
application of very high gas pressure onto the wafer surface,
resulting in an extrusion-like motion of the film into deeper
features. If SOM exceeds the step height, the top surface of
the solution is plain. Shrinkage does not depend on thick-

FIG. 4. SEM cross sections showing the step coverage of spin-on Cu: 共a兲
FIG. 2. TEM picture of SOM solution. 250-nm-thick Cu, 共b兲 700-nm-thick Cu, and 共c兲 1300-nm-thick Cu.

J. Vac. Sci. Technol. B, Vol. 17, No. 5, Sep/Oct 1999

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 2323 Murakami et al.: Spin-on Cu films for ULSI metallization 2323

FIG. 5. SEM cross-section view of Cu-filled trenches.

effect. Trenches 共Fig. 5兲 and 0.3 ␮m via with an aspect ratio

of ⬎3:1 were filled defect free 共Fig. 6兲.
This bottom-up process is also useful in other Cu deposi-
tion processes, for example, Cu seed layers for plasma vapor
deposition 共PVD兲 and ECD. ECD Cu on a PVD Cu seed
structure has already been used in actual fabrication.6,7 Cur-
rently, the seed layer deposited by standard sputtering often
gives rather poor step coverage. Improved seed layer step
coverage is needed for smaller geometries with a higher as-
pect ratio. One answer is the SOM process. The step cover-
age achieved with the SOM process is shown in Fig. 7. The
very thin Cu film near the top prevents closing at the top and
enhances film thickness at the sidewalls and bottom. Figure 8
shows the filling profile of SOM-ECD integration for trench
0.18 ␮m wide with an aspect ratio exceeding 5:1. Spin-on
FIG. 7. SEM cross-sections showing the Cu seed layer deposited by the
SOM process.
Cu can provide good step coverage; however, adhesion to
the barrier layer remains an issue in ECD. For this process,
further interface study is needed to improve adhesion prop-
erty to the substrate.
The peeling strength in the tape-peeling test was esti-
mated to be 3 kg/mm2. No failure was seen. Although we
could not reliably determine adhesion strength in this test,
we can say that the results of the adhesion tests for spin-on

FIG. 8. SEM cross section showing the filling profile of SOM-ECD integra-
FIG. 6. SEM cross-section view of 0.3 ␮m Cu-filled via (AR⬎3:1). tion for a high-aspect ratio trench.

JVST B - Microelectronics and Nanometer Structures

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 2324 Murakami et al.: Spin-on Cu films for ULSI metallization
Cu films showed relatively high adhesion. Spin-on Cu films
deposited on sputtered TiN have a 共111兲 orientation. For 0.3
␮m thick spin-on Cu film, an x-ray intensity ratio of 共111兲
and 共200兲 planes, I(111)/I(200), is 6.2. Since I(111)/I(200)
is less than 2.2 for randomly oriented Cu powders, the tex-
ture of spin-on Cu films on TiN is strongly 共111兲 oriented.
The thickness of spin-on Cu films was determined by a SEM
cross-section view. Sheet resistance of spin-on Cu films was
measured using a four-point probe. Thickness uniformity of
spin-on Cu films on 8 in. wafers was in ⬃1%, 3␴, and the
electrical uniformity was in a similar range as thickness uni-
formity. Resistivity below 2.0 ␮⍀ cm was obtained when
spin-on Cu films exceeded 500 nm in thickness. Contamina-
tion in Cu film was analyzed by SIMS, but no metal con-
tamination was seen.
IV. SUMMARY
We developed new spin-on techniques, SOM, to enhance
Cu deposition at the bottom of trenches and vias. It has the
J. Vac. Sci. Technol. B, Vol. 17, No. 5, Sep/Oct 1999
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2324
advantages of using no seed layer, providing excellent uni-
formity and good via/trench filling, and being inexpensive.
Step coverage exceeding 100% for spin-on Cu allows us
defect-free filling of sub-0.5 ␮m features such as 0.3 ␮m
wide trenches and 0.3 ␮m size vias with a high aspect ratio
of up to 3:1. Sheet resistance of spin-on Cu films was less
than 2.0 ␮⍀ cm. We verified the applicability of spin-on Cu
for the ECD seed layer, but further interface study is needed
to improve adhesion property.
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