Microstructure analysis of plasma enhanced atomic layer deposition-grown mixed-

phase RuTaN barrier for seedless copper electrodeposition

Tonmoy Chakraborty and Eric T. Eisenbraun

Citation: Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 30, 020604 (2012); doi:
10.1116/1.3684597
View online: http://dx.doi.org/10.1116/1.3684597
View Table of Contents: http://avs.scitation.org/toc/jva/30/2
Published by the American Vacuum Society
Microstructure analysis of plasma enhanced atomic layer deposition-grown
mixed-phase RuTaN barrier for seedless copper electrodeposition
Tonmoy Chakrabortya) and Eric T. Eisenbraun
College of Nanoscale Science and Engineering, University at Albany, State University of New York, 257,
Fuller Road, Albany, New York 12203
(Received 20 December 2011; accepted 25 January 2012; published 10 February 2012)
Plasma enhanced atomic layer deposition (PEALD)-grown mixed phase RuTaN films has been stud-
ied as a direct plate material for Cu electroplating within interconnects. It was seen that these liners
behaved as excellent Cu diffusion barrier and could be scaled down to sub-5 nm thicknesses. High re-
solution TEM based structural analysis of these films showed islands of Ru surrounded by amorphous
region. The selected area electron diffraction pattern corresponds to the hcp phase of Ru with (101)
as the primary crystallographic orientation. Scanning tunneling microscopy and atomic force micros-
copy suggested the VolmerWeber growth mechanism of these liners. A series of electroplating
experiments with various plating current density and time showed that a uniform bottom-up filling
could be achieved in trenches with RuTaN as direct plate liners. Trenches with aspect-ratio as high
as 10 could be filled uniformly. The conformality of the PEALD RuTaN process within the trenches
was also found to be very promising with step-coverage over 85%. V C 2012 American Vacuum

Society. [DOI: 10.1116/1.3684597]

I. INTRODUCTION
Copper electrochemical deposition (ECD) in interconnects
has traditionally been carried out by employing a sputtered
copper-seed layer to improve plated copper adhesion, micro-
structure, and electromigration characteristics.1 The use of cop-
per in interconnect metallization requires the use of a barrier
layer to prevent the diffusion of Cu into the dielectric below as
well as an adhesive layer and a thin copper seed layer.2,3 The
most popular choice for a copper barrier/seed stack is a trilayer
consisting of physical vapor deposition (PVD)-grown Cu (seed)
on top of a Ta layer as adhesion layer and TaN as a barrier.4,5
This stack is necessarily complex and relatively thick, and as
such, the intrinsic drawbacks of the PVD process employed for
the growth of the stack may present scalability issues in upcom-
ing interconnect geometries where a continuous and ultrathin
diffusion barrier (5 nm thick or less) will be required.1 Hence a
robust diffusion barrier layer that has intrinsic copper direct
plate and adhesion characteristics is desirable for emerging
interconnect applications because it removes the need for sepa-
rate adhesion and seed layers.5,6 Materials such as TaN are
excellent Cu diffusion barriers but do not support direct electro-
deposition of copper.79 Recently, Ru has generated a lot of in-
terest in the research community for its potential use as a direct
plate material and nucleation layer for the ECD copper.1012
This is a direct result of various extraordinary properties of Ru
like its low bulk resistivity (7.1 lX cm), a high melting point
(2310  C) and negligible solubility in Cu even at 1000  C.12,13
Also, plated Cu is known to have excellent adhesion and wett-
ability to Ru.12 However, due to the columnar microstructure,
Ru fails to act as Cu diffusion barrier.14
In the past few publications this group has successfully used
the properties of both Ru and TaN to manufacture a viable so-
lution for a thinner, yet effective direct plate barrier.1517 A
plasma enhanced atomic layer deposition (PEALD) technique
a)
Electronic mail: tchakraborty@uamail.albany.edu
was used to deposit such films. It was found that the properties
of these mixed phase films were a strong function of the Ru to
Ta ratio in the film. In particular, films with Ru:Ta 12:1
appear to be particularly well suited for combined direct plate
liner properties, and it was found that these films could prevent
copper diffusion with similar performance to TaN. When
plated on blanket films the deposited copper not only showed
high nucleation density but, also was found to have a high
(111) texture.16,17 The growth of the plated copper on blanket
RuTaN films was found to follow a cluster growth mechanism,
with nucleation closely following a 3D-type mechanism. These
PEALD-grown RuTaN films showed extendibility to 23 nm
thickness in terms of their direct plating properties.
This manuscript is primarily focused on a study of the
microstructure of these RuTaN films. The structural informa-
tion of these liners is critical for developing an understanding
of the science behind the performance of these barriers. Also
discussed in this paper are experiments with various plating pa-
rameters to optimize the filling charecteristics inside trenches.
II. EXPERIMENT
The RuTaN films were deposited by applying alternating
PEALD sequences of Ru and TaN using a 200 mm capable
wafer processing PEALD tool described previously.16,17 Si
with a 140 nm thick deposited SiO2 layer was used as the sub-
strate. The thickness and composition of the RuTaN films
were controlled using the number of individual ALD cycles of
Ru and TaN, as described in prior publications.15,17 Ethylcy-
clopentadienyl pyrrolyl ruthenium was used as a precursor gas
for Ru growth, while tert-butylimino-tris(diethylamino) tanta-
lum was used for TaN. Unless otherwise indicated, 4 nm thick
PEALD RuTaN films with a nominal 12:1 Ru:Ta metal ratio
were used for all experiments discussed herein.
The barrier composition was determined by using a
Thermo VG-Scientific theta probe x ray photoelectron spec-
troscopy (XPS) system featuring a monochromated Al Ka

020604-1 J. Vac. Sci. Technol. A 30(2), Mar/Apr 2012 0734-2101/2012/30(2)/020604/5/$30.00 C 2012 American Vacuum Society
V 020604-1
020604-2 T. Chakraborty and E. T. Eisenbraun: Microstructure analysis of PEALD-grown mixed-phase RuTaN barrier
x ray source (1486.6 eV) and pass energy resolution of
100 eV. In addition to the XPS, Rutherford back-scattering
spectrometry (RBS) was also performed to estimate the com-
position of these PEALD liners. These RBS measurements
were performed on a Dynamitron linier particle accelerator.
To reduce the effects of surface oxidation due to air expo-
sure, these films were annealed at 150  C in a forming gas
(95% Ar and 5% H2) environment at a pressure of 600
Torr for 15 min as a precleaning step before plating. A dc
electroplating system with a sacrificial anode was used to
carry out electroplating. The potential was regulated with a
programmable power supply, PDPR10-1-3 series with plater
control terminal (Dynatronix Inc.). The plating bath was
made up of 0.8 M of H2SO4, 0.8 M of CuSO4
5H2O, and
1.4 mM of HCl. To make the chemistry as close as possible
to a commercial plating bath, a chemical additive package
(ViaForm, Enthone, Inc.) was added, including accelerator
(9 ml/l), leveler (2 ml/l), and suppressor (2.5 ml/l). A range
of plating current densities (210 mA/cm2) and plating times
(1545 s) was used to electrodeposit Cu in order to capture
the initial nucleation and growth features of the plated Cu on
the RuTaN liners. These experiments were carried out on a
multiline-width trench structure. Following the liner and
electroplated Cu deposition, the samples were cryo-cooled
and cleaved to expose the cross-section. This allowed view-
ing of the Cu nucleation inside the trenches. A LEO 1550
field emission scanning electron microscope was used to
investigate the details of the Cu nucleation.
In order to understand the microstructure of these liners an
extensive TEM analysis was carried out. Various sample prepa-
ration techniques were used for the TEM analysis. Preparing a
plan-view TEM sample can be challenging, since the layer of
interest is very thin, but it must be noted that during TEM sam-
ple preparation, this thin layer can be changed, contaminated or
destroyed. Hence special care was taken while preparing such
samples. The specimen was prepared by thinning (ion milling)
the sample from the backside of the substrate and protecting
the front side by means of a metal cap. The sample was thinned
to TEM transparency. The final shape of the TEM specimen
forms a wedge. This gradient in thickness allows the optimum
thickness to be chosen for a particular TEM study. Several FIB
cut samples (cross-sectional viewing) were also prepared to
look for the conformality of RuTaN liners inside the trenches.
The TEM analysis was performed on a JEOL 2010F with a
Schottky field emitter source operated at 200 keV.
The surface topography of these liners was measured using
scanning tunneling microscopy (STM) and atomic force micros-
copy (AFM). The STM images were acquired at 77 K on a 2 lm
 2 lm scan area with constant tunneling current of about 0.1
nA and a tip bias of about 2.5 V. These tunneling parameters
were found to give the best image quality, and systematic bias
dependent imaging was not performed. AFM scan were per-
formed on a similar scan area as that of STM using a Veeco
Autoprobe CP-Research system operated in tapping mode.
III. RESULTS
Figure 1 shows the high resolution bright field TEM micro-
graph of a plan-view 5 nm thick PEALD TaN sample. No
J. Vac. Sci. Technol. A, Vol. 30, No. 2, Mar/Apr 2012
020604-2
FIG. 1. High resolution TEM micrograph of a plan-view 5 nm thick PEALD
TaN sample. Inset: SAED pattern confirming amorphous nature of TaN.
grains, grain boundaries or crystalline fringes were observed,
which suggests that the deposited PEALD TaN films are amor-
phous with no trace of crystallinity. The selected area electron
diffraction (SAED) pattern shown in the inset of Fig. 1 also
confirms this finding. When a 5 nm PEALD pure Ru sample
[Fig. 2(a)] is viewed top-down under a HRTEM, Ru nanocrys-
talls could be clearly seen. A higher resolution image, Fig.
2(b), shows Ru in polycrystalline form with lattice fringes.
The SAED image shows a ring pattern, which confirms the
polycrystalline nature of these PEALD Ru films. When calcu-
lated for texture, it was found that the SAED pattern of these
direct plate liners correspond to the hcp phase of Ru with
(101) as the primary crystallographic orientation.
RuTaN films with metal ratio 12 are of particular interest
because they are conductive enough to directly plate and
retain their Cu diffusion barrier property. One can see that
such films show the presence of both crystalline and amor-
phous regions, as in Fig. 3(a). Lattice fringes could also be
seen clearly in the higher resolution images [Fig. 3(b)]. Figure
3(c) shows that the SAED ring patterns from the RuTaN films
correspond exactly to the pure Ru film. This confirms that the
crystallinity of these RuTaN films is solely due to the Ru
phase while the TaN remains amorphous in the film. Also it
should be noted that the Ru phase in the RuTaN film remains
unaltered compared to the pure Ru sample, which suggests
that the incorporation of TaN into the film did not result in
any new phase generation by intermixing with Ru nano-
crystals. However, it is yet to be determined if any amorphous
Ru is incorporated in the amorphous TaN.
Study of the surface topography is an integral part of the
structural analysis of the films. Scanning tunneling microscopy
(STM) was carried out on these liners. 5 nm thick PEALD Ru,
RuTaN and TaN liners were deposited on 100 nm SiO2 wafer.
Figure 4(a) shows the STM image of a pure Ru film. One can
see densely packed spherical features constituting the film,
suggesting VolmerWebber growth mechanism.18 A 2 lm
 2 lm area-scan on these films shows that the rms roughness
of these films is about 0.21 nm. Comparison of the HRTEM
and STM image clearly shows that the spherical features in
STM image correspond to the grains in the TEM microstruc-
ture. When a pure TaN film was used for a similar analysis it
was found that owing to the higher resistivity of the film the
020604-3 T. Chakraborty and E. T. Eisenbraun: Microstructure analysis of PEALD-grown mixed-phase RuTaN barrier
FIG. 2. (a) HRTEM image of a 5 nm Ru sample showing Ru nano-crystals,
(b) higher resolution image showing lattice fringes. Inset: SAED pattern
confirming crystallinity and texture of Ru film.
STM tunneling current could not be obtained. The RuTaN
films (metal ratio 12) on the other hand are conducting
enough to allow the tunneling current to be measured. With a
tunneling current of 1 nA the image shown in Fig. 4(b) was
obtained. A similar granular structure was obtained for RuTaN
films, only this time, the size distribution of the spherical fea-
tures appears to be higher. The rms roughness on the RuTaN
film is about 0.67 nm. The corresponding AFM scans for pure
Ru and RuTaN gave an rms roughness of 0.27 and 0.73 nm.
An interesting fact to note here is the striking agreement in the
rms roughness values of the two different measurement techni-
ques. This suggests that the local electronic properties of the
crystalline and the amorphous region do not affect the value of
rms roughness in the STM measurement.
The ultimate aim of these direct plate liners is to be able to
use them as a possible replacement for the existing tri-layer
structures (diffusion barrier/adhesion promoter/Cu seed) in
JVST A - Vacuum, Surfaces, and Films
020604-3
FIG. 3. (a) HRTEM image of RuTaN film showing both crystalline and
amorphous region, (b) higher magnification image showing lattice fringes,
(c) SAED pattern of RuTaN films as compared to the pure Ru pattern.
upcoming interconnect technology nodes. To determine initial
utility of these direct plate liners in patterned damascene-type
structures, PEALD RuTaN (Ru:Ta12, thickness 4 nm) films
were deposited in trench structures to understand and control
the plating process. As a result a series of plating experiment
were carried out with various plating time and current den-
sities. Figure 5(a) shows the plating profile obtained using a
constant current density of 2 mA/cm2 for 20 s. Nucleation of
Cu on such films under these conditions were found to be non-
uniform with large Cu nuclei hindering the trench filling.
When the current density was increased to a higher value of
5 mA/cm2, again with a plating time of 20 s, it was found
[Fig. 5(b)] that the size of the Cu nuclei decreased remark-
ably. One can also see the Cu nuclei sticking on to the
sidewalls of the trenches and filling the trenches from the bot-
tom. When the plating current density was increased to
6.5 mA/cm2 and the time of plating to 30 sec it could be seen
that the trench filling was a bit more complete with Cu nuclei
020604-4 T. Chakraborty and E. T. Eisenbraun: Microstructure analysis of PEALD-grown mixed-phase RuTaN barrier 020604-4

FIG. 5. (Color online) Plating profile obtained using a constant current den-
sity of (a) 2 mA/cm2 for 20 s, (b) 5 mA/cm2 for 20 s, (c) 6.5 mA/cm2 for
30 s, and (d) 10 mA/cm2 for 25 s. It can be seen that with increasing current
density the size of the Cu nuclei seemed to be decreasing and the bottom-up
filling could be gradually obtained.
FIG. 4. (Color online) Scanning tunneling microscope image of PEALD-
grown (a) Ru film (5 nm thick) showing VolmerWeber growth mecha- on top of the trench (4.6 nm) to the minimum thickness
nism (b) RuTaN film (5 nm thick) showing similar features as that of the
Ru film; however, the distribution of the granular structure appears to be (4 nm) of the film within the trench, showed that the step
larger than the pure Ru film. coverage of the process was greater than 85%, demonstrating
the promise of plasma assisted process in conformal growth
still adhering to the side walls of the trenches [Fig. 5(c)]. behavior.
Followed by this a higher current density of 10 mA/cm2 for
25 s was used, and as can be seen in Fig. 5(d), a uniform plat- IV. CONCLUSION
ing profile was obtained with a bottom-up filling. A uniform
and complete filling could be achieved with such a plating A PEALD process for the growth of a novel mixed-phase
condition on features with aspect ratio as high as 10, shown in RuTaN barrier, developed for advanced interconnect metalli-
Fig. 6, suggesting the potential use of these liners in through zation applications, has been studied with respect to its struc-
silicon vias (TSV). tural and plating properties. A TEM based study showed that
One of the main reasons for using a mixed-phase barrier is the microstructure of these RuTaN films are made up of a
the ability to completely fill sub-50-nm structures in the ab-
sence of any underlying adhesion promoter and seed layer,
which avoids the scalability concerns associated with the tri-
layer stack configuration presently used for interconnect struc-
tures. In order to do so a conformal deposition of the PEALD
liners within the trenches is desirable. A nonconformal liner
could result in failure to prevent Cu diffusion into the sub-
strate. It could also cause a variation in local resistivity,
thereby resulting in voids caused by a nonuniform Cu plating
profile. A 5 nm thick film with a Ru:Ta ratio of 12 was de-
posited over a patterned structure containing sub-45 nm wide
trenches. Followed by this the trenches were filled using an
ECD Cu deposition technique. The plating was carried out for
40 s using a constant current-density of 10 mA/cm2. Figure 7
FIG. 6. (Color online) Plating profile obtained in a high aspect ratio feature
is a HRTEM image of a FIB cut TEM sample generated for trench (AR10) using a 10 mA/cm2 plating current density. One can see a
cross-sectional viewing. A comparison of the film thickness uniform bottom up filing was achieved with no voids.

J. Vac. Sci. Technol. A, Vol. 30, No. 2, Mar/Apr 2012

020604-5 T. Chakraborty and E. T. Eisenbraun: Microstructure analysis of PEALD-grown mixed-phase RuTaN barrier
FIG. 7. (a) Cross-sectional TEM image of 45 nm trenches with PEALD-
grown RuTaN films. The target thickness of the film was 5 nm. The trenches
were filled with Cu using ECD with a constant current density of 10 mA/cm2
for 40 s. Conformality of the PEALD-grown RuTaN films within the trenches.
(b) Higher magnification TEM image of the trench obtained by stitching sev-
eral pictures of the same trench.
combination of nanocrystalline and amorphous phase with
the crystalline phase in RuTaN films matching exactly to
that present in pure Ru films. However further study is
needed to determine whether the amorphous phase is made
up of just amorphous TaN or a combination of amorphous
Ru and amorphous TaN. The surface topography, as seen by
STM and AFM measurements, of these PEALD RuTaN
films show VolmerWeber growth mechanism with rms
roughness as measured by both techniques closely matching
JVST A - Vacuum, Surfaces, and Films
020604-5
each other. Short pulse plating experiments performed in
trenches revealed that 10 mA/cm2 current density results in a
bottom-up filling of plated Cu. Using these PEALD RuTaN
liners, trenches with aspect ratio as high as 10 could be filled
properly. A TEM based measurement shows that the confor-
mality of these liners is about 85%, which confirms the via-
bility of the PEALD process.
ACKNOWLEDGMENTS
This research was supported by the Semiconductor
Research Corporation (SRC) and the New York State Foun-
dation for Science, Technology and Innovation (NYSTAR)
under the New York Center for Advanced Interconnect Sci-
ence and Technology (NY-CAIST).
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