JOURNAL OF APPLIED PHYSICS VOLUME 88, NUMBER 4 15 AUGUST 2000

The role of kinetics in the nucleation and void formation in copper films
produced by chemical vapor deposition
R. Kröger,a) M. Eizenberg, and E. Rabkin
Department of Materials Engineering, Technion-Israel Institute of Technology, 32000 Haifa, Israel
D. Cong and L. Chen
Applied Materials Inc., Santa Clara, California 95054
共Received 24 January 2000; accepted for publication 8 May 2000兲
The heterogeneous nucleation and subsequent growth of chemical vapor deposited copper using
hexafluoroacetylacetonate-Cu共I兲-trimethylvinylsilane on physical vapor deposited tantalum and
chemical vapor deposited titanium nitride was studied by means of electron microscopy and atomic
force microscopy. It was found that the nucleation densities are about two orders of magnitude
higher on TiN than on Ta. This leads to an increased roughness of films deposited on Ta compared
to those produced on TiN. Moreover, the Cu films on the Ta substrate show a large number of voids,
whereas no such voids were observable in the Cu films deposited on top of TiN. A simplified model
for the influence of gas-surface reaction and surface self-diffusion on the shape of the Cu grains was
developed. This model, which is supported by the experimental data, shows that if the grain shape
changes from spherical to nonspherical before coalescence with neighboring grains, voids occur. A
critical grain size and nucleation density of about 150 nm and 5⫻1013 m⫺2, respectively, were
calculated for the deposition conditions used in this work. © 2000 American Institute of Physics.
关S0021-8979共00兲01816-8兴

I. INTRODUCTION especially for the deposition of CVD Cu films in narrow

Replacing Al共Cu兲 by Cu in microelectronic interconnect
technology is a process that gains momentum since the first
report of the introduction of Cu in advanced devices in
1997.1 With the trend of shrinking device dimensions, the
use of chemical vapor deposition 共CVD兲 for the production
of Cu films for interconnect metallization in microelectronics
is becoming more and more interesting. This is due to the
excellent step coverage and selectivity that can be achieved
by this method.2 Nevertheless, to develop CVD as a techno-
logically reliable tool for Cu metallization requires a distinct
knowledge and controllability of the interactions that can
take place between the diffusion barrier and the Cu film. The
currently best known precursor for CVD Cu deposition,
which combines relative thermal stability and low tempera-
ture deposition conditions, is hexafluoroacetylacetunate-
Cu共I兲-trimethylvinylsilane 关hfac-Cu共I兲-tmvs兴, also known as
Cupraselect™.
The nucleation and initial grain growth is the most im-
portant step to be understood in the process of film forma-
tion. It is well established that the substrate material has a
great influence on the nucleation since the disproportionation
reaction of the precursor is catalytically enhanced and thus
sensitive to the electronic and morphological structure of the
substrate.3,4
The presented work focuses on the quantification of the
nucleation process and is aimed at a better understanding of
nucleation related phenomena such as the formation of voids
in the coalesced films and the influence of nucleation on the
surface roughness of the resulting films. This is important
a兲
Electronic mail: kroeger@tx.technion.ac.il
trenches where these phenomena affect sensitively properties
like adhesion, conductance, and electromigration resistance.
Two barrier materials were selected for this investiga-
tion: Ta, which was produced by a physical vapor deposition
共PVD兲 process and TiN, deposited using metalorganic CVD.
The former is the best known Cu barrier for the time being,
whereas the latter is a promising candidate for the introduc-
tion of a CVD diffusion barrier.
II. EXPERIMENTAL DETAILS
The film preparation was performed in an Endura™
cluster tool as described in our previous publication.2 This
setup enables the integrated deposition of PVD Ta or CVD
TiN barrier and Cu layers without air exposure. The CVD Cu
deposition was performed using hfac-Cu共I兲-tmvs at 453 K
substrate temperature, 6.5 Pa total pressure, and 0.65 Pa pre-
cursor partial pressure. These where found to be the optimal
values to obtain high deposition rates and good step cover-
age, which are important for the application in the dual
damascene process. To study the initial growth stage and
film evolution on the different barrier materials, CVD Cu
film growth was performed in a time range between 90 and
420 s on either the sputtered Ta or the CVD TiN layer. These
deposition times lead to CVD Cu films of nominally 10–150
nm thickness. The CVD TiN layer was prepared by deposi-
tion of a TiCN layer using tetrakis-dimethyl-amido-titanium
and subsequent crystallization and carbon removal by an
Ar/H2 plasma.5 In a two step deposition process a stack of
two layers, 5 nm each, of CVD TiN was produced.
Atomic force microscopy 共AFM兲 was applied to study
the normal size distribution of the discrete Cu grains as well

0021-8979/2000/88(4)/1867/6/$17.00 1867 © 2000 American Institute of Physics

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1868 J. Appl. Phys., Vol. 88, No. 4, 15 August 2000
FIG. 1. CVD Cu deposition on PVD Ta 共a兲共c兲 and CVD TiN 共b兲, 共d兲 for 90
and 150 s.
as the surface topography of the coalesced films. The lateral
size distribution of these grains was obtained by using high-
resolution scanning electron microscopy 共HRSEM兲, which
also served to investigate the voids in the coalesced films.
The interface between the Cu and the barrier was studied
using conventional as well as high-resolution transmission
electron microscopy 共CTEM/HRTEM兲.
III. RESULTS AND DISCUSSION
A. CVD Cu Nucleation on PVD Ta and CVD TiN
The initial growth of the CVD Cu grains after a deposi-
tion time of 90 s on Ta and TiN was investigated by HRSEM
关see Figs. 1共a兲–1共d兲兴. A significant difference in grain den-
sities is observed, which may be attributed to the different
nucleation rates of the CVD Cu on each barrier material. On
Ta a nucleation density of about 1013 m⫺2 is observed,
whereas on the TiN layer a nucleation density of about
1015 m⫺2 is obtained. Two possible reasons could be respon-
sible for this difference: 共a兲 the Ta film is less chemically
reactive towards the CVD precursor, possibly due to the for-
mation of an oxide surface layer during the early stages of
growth; 共b兲 the significantly higher surface roughness of the
TiN 共3.5 Å compared to 1.5 Å for Ta, as measured by AFM兲
supports nucleation at steps and edges. AFM images of CVD
Cu films deposited for 90 s are displayed in Figs. 2共a兲 and
2共b兲. The histograms of these images—also shown in this
figure—reveal that the average height of the grains on Ta is
about 4 nm, much lower than the average grain height of
about 10 nm on top of TiN for the same deposition time.
Furthermore, it can be seen that secondary nucleation is neg-
ligible, since a sharp and symmetric size distribution is ob-
servable at this stage. These findings are confirmed by TEM.
Figures 3共a兲 and 3共b兲 show HRTEM cross sectional images
of CVD Cu deposited for 共a兲 150 s on Ta and 共b兲 90 s on
TiN. The grains formed at the shortest deposition time are
spherical 关Fig. 3共a兲 for TiN and similarly for Ta—not shown
here兴 and show no wetting on the barrier layer in both cases.
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Kröger et al.
FIG. 2. AFM images and histograms of the topography of CVD Cu grains
after 90 s deposition time on 共a兲 PVD Cu and 共b兲 CVD TiN.
The spherical shape of the grains is due to a minimization of
surface energy at this grain size. It can also be seen that the
grains formed on the Ta barrier for 150 s 关Fig. 3共b兲兴 deviate
from a spherical shape. The poor wetting can be related to
the formation of a contamination layer at the early stages of
growth which contains fluorine, oxygen, and carbon, a phe-
nomenon described in detail in one of our previous
publications.6 The island type growth observed here results
in a random orientation of the polycrystalline Cu film formed
after coalescence. The height and lateral size of the grains,
observed by cross sectional HRTEM, agree well with the
values found by HRSEM and AFM.
Based on the data of the lateral size 共HRSEM兲 and
height 共AFM兲 distribution the actual molar deposition as a
function of time was determined 共see Fig. 4兲. The insert in
Fig. 4 shows the plot of molar deposition up to 420 s. It can
be seen that nucleation occurs after some incubation time
due to the difficulty of the heterogeneous Cu formation. This
incubation time is longer for Ta than for TiN. To estimate
the sticking coefficient on the different barrier materials the
ratio ␤ ⫽R dep/2R arr was calculated. R dep is the deposition
rate, and R arr is the arrival rate of precursor molecules on the
surface. The factor 2 in this expression stems from the fact
FIG. 3. HRTEM cross-sectional images of CVD Cu grains 共a兲 after 90 s
deposition on CVD TiN and 共b兲 after 150 s deposition on PVD Ta.
J. Appl. Phys., Vol. 88, No. 4, 15 August 2000
FIG. 4. Molar deposition as function of time on PVD Ta and CVD TiN as
determined from HRSEM and AFM images. The insert shows the molar
deposition up to a deposition time of 420 s.
that two precursor molecules are necessary to from one de-
posited Cu atom. From the kinematic theory we obtain
p prec
R arr⫽ , 共1兲
共 2 ␲ M preck B T 兲 1/2
where p prec and M prec are the precursor partial pressure and
molar weight, T the temperature, and k B is the Boltzmann
constant. The resulting value of ␤ gives an upper limit for
the nucleation density since the critical nucleus size is un-
known and the method does not reveal stable clusters that
consist only of a few atoms. Thus, instead of R dep , we use
␴ i / ␶ with ␴ i being the respective observed grain density and
␶ the shortest deposition time 共90 s兲. Inserting the character-
istic values we obtain ␤ Ta⬍10⫺6 and ␤ TiN⬍10⫺4 . This ex-
plains also why secondary nucleation is less likely, since it is
known that the sticking coefficient of Cupraselect™ on Cu is
at least two orders of magnitude higher than the values ob-
tained on TiN.7,8
B. Surface roughness
The surface roughness of the deposited films was studied
using AFM and determining the rms values of the topo-
graphical images. Figure 5 shows the results of these mea-
surements. Two time intervals can be distinguished in this
graph: 共a兲 one interval below 150 s before the grains coalesce
and form a coalesced film and 共b兲 the second interval above
150 s in which the film grows. The rms values for interval 共a兲
are clearly different for the films deposited on Ta and those
produced on TiN. Due to the lower nucleation density of
CVD Cu on Ta, only a few islands are formed in the begin-
ning explaining the low rms value. Upon merging relatively
large crystallites and facets are formed and thus an increase
in roughness is observed. Since the nucleation on TiN is
much easier, the high nucleation density enables a merging
of crystals during grain growth of much smaller grains, ex-
plaining the lower roughness values obtained on TiN above
150 s. Therefore, the nucleation density affects the roughness
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Kröger et al. 1869
FIG. 5. Surface roughness as function of deposition time for CVD Cu de-
posited on PVD Ta and CVD TiN.
of the subsequently deposited film, even for films as thick as
150 nm, as evidenced by the higher rms value on Ta than on
TiN.
C. Void formation
HRSEM micrographs of the backside of CVD Cu films
deposited on Ta and TiN of about 150 nm thickness are
shown in Figs. 6共a兲 and 6共b兲. These films were detached
from the barrier using an adhesive tape. The Cu film depos-
ited on Ta 关Fig. 6共a兲兴 exposes a high density of voids, sized
between 10 and 100 nm. As can be seen in the CTEM cross
sectional image of such a void, given in Fig. 7共a兲, it is
hemispherical-with a radius of about 50 nm. Also, CVD Cu
films deposited on TaNx 共not shown here兲 show such kind of
voids but with a somehow lower density.2 In the Cu depos-
ited on TiN 关Figs. 6共b兲 and 7共b兲, respectively兴 no voids are
observable, and the Cu film backside only reflects the higher
surface roughness of the TiN compared to Ta. In the follow-
ing section a simple model to explain the phenomenon of
void formation and its dependence on the nucleation density
is proposed.
D. Model of void formation
The correlation between void formation and low nucle-
ation density combined with the observed formation of ‘‘dis-
torted’’ grains before film merging enabled us to propose a
simple model. In this model, the formation of voids is pre-
FIG. 6. HRSEM images of the backside of CVD Cu films deposited on 共a兲
PVD Ta and 共b兲 CVD TiN.
1870 J. Appl. Phys., Vol. 88, No. 4, 15 August 2000 Kröger et al.

is the Avogadro number. We assume that the chemical po-

tential changes from this maximal value at the top of the cap
to zero on the flat surface, along a distance of the order of r.
The driving force for surface diffusion, F, which is simply
the gradient of the chemical potential, is thus given by10
2␥V0
F⫽ . 共2兲
r2
The atomic flux is determined by the product of the driving
force F and the surface diffusion mobility
Ds
J A ⫽F , 共3兲
k BT
where D s is the coefficient of surface self-diffusion. The to-
tal flux due to surface diffusion results from the integral over
the flux area

J tot⫽ 冕 P
J A ds⫽
4 ␲ ␦ ␥ D sV 0 1
k BT r
, 共4兲

where ␦ is the thickness of one atomic layer on the surface

where diffusion occurs. The volume change with time caused
by smoothing is given by

FIG. 7. CTEM cross-sectional images of about 150-nm-thick CVD Cu layer

on top of 共a兲 PVD Ta and 共b兲 CVD TiN. 冉 冊
⳵V
⳵t s
⫽2 ␲ r 2
⳵r
⳵t 冉 冊 s
. 共5兲

Using the obvious relationship J tot⫽⳵V/⳵t and Eq. 共4兲 we

ceded by the loss of stability of the ideal spherical shape of obtain

growing grains. Figure 8 depicts the basic assumptions of
this model. It is assumed that on the Cu grain surface a
perturbation may occur due to local deviation of the growing
Cu grain from a spherical shape. Such a perturbation will
grow further if the tendency for growth 共caused by a concen-
tration gradient in the gas phase兲 is stronger than the ten-
dency for smoothing 共due to the curvature-driven surface dif-
fusion兲. We assume here a simple cap shaped perturbation
having a volume of (2/3) ␲ r 3 . According to Herring,9 the
curvature-related contribution to the chemical potential of
atoms on the top of the cap is given by 2 ␥ V 0 /r, where ␥ and
V 0 are the surface energy and the atomic volume, respec-
tively. The latter can be estimated from M Cu( ␳ CuN A ) ⫺1 ,
where M Cu is the molar weight of Cu, ␳ Cu its density, and N A
冉 冊
⳵r 2 ␥ ␦ D sV 0
⫽ . 共6兲
⳵t s k B Tr 3
Therefore, the rate of perturbation smoothing due to the sur-
face diffusion is proportional to r ⫺3 , and thus, it decreases
rapidly with increasing cap size.
The tendency for perturbation smoothing competes with
the tendency for growth due the finite deposition rate at the
surface. The deposition process is affecting the concentration
profile of precursor species in the gas phase such that it leads
to the formation of a concentration gradient due to the dis-
appearance of precursor at the surface. We assume a simple
first order reaction following the kinetics R⫽Kc prec 共R:
growth rate, c prec : precursor concentration, and K: reaction
rate兲. If the effect of a small perturbation on the concentra-
tion distribution in the gas phase is neglected, the perturba-
tion growth is only due to the fact that the deposition rate is
higher at the top of the cap than at the grain surface. A
similar effect, the so called ‘‘flux focusing,’’ is reported in
the literature for the case of solidification from the liquid
phase.11 Based on these assumption the perturbation growth
rate can be described by

冉 冊
⳵r
⳵t g
⫽K
⳵ c prec
⳵z
r 共7兲

with r being the height difference between the top of the

FIG. 8. Illustration of the model that is used to discuss the void formation.
J dep is the flux of precursor molecules leading to Cu formation on the sur-
face, J A is the flux of Cu atoms due to the curvature driven surface diffu-
sion, r is the radius of the perturbation, and ␦ the thickness of one atomic
layer.
perturbance and the grain surface. The overall growth rate is
estimated as being proportional to half of the gas phase dif-
fusion flux of precursor molecules to the surface R⫽J diff/2
共since two Cupraselect™ molecules are needed to create one

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J. Appl. Phys., Vol. 88, No. 4, 15 August 2000
FIG. 9. Smoothing rate ( ⳵ r/ ⳵ t) s and growth rate ( ⳵ r/ ⳵ t) g of a perturbation
as function of perturbation size r.
copper atom兲. This estimation is justified by the high precur-
sor conversion efficiency of about 50%, which is due to the
high precursor reactivity on Cu. These assumptions lead to
⳵ c prec
R⫽ 12 D g V0 ,
⳵z
where D g is the diffusion coefficient of the precursor in the
gas phase that can be calculated based on the theory of Chap-
man and Enskog.11 Substitution of Eq. 共8兲 into Eq. 共7兲 and
estimating K from R/c 0 (c 0 is the initial precursor concen-
tration, R is experimentally found to be typically about 1
nm/s兲 gives
冉 冊
⳵r
⳵t g
⫽
2R 2
c 0D gV 0
r.
Hence, it is expected that the growth rate of a perturbation is
proportional to r. In Fig. 9 the obtained rates for smoothing
and growth, as determined from Eqs. 共6兲 and 共9兲, respec-
tively, are plotted as a function of r. The coefficients and
parameters were taken from literature.12,13 In Table I the val-
ues, used to calculate these curves, are shown. The two
curves intersect at a critical radius given by
r c⫽ 冉 V 20 ␥ ␦ D g D s c 0
k B TR 2
冊 1/4
. 共10兲
A value of about 150 nm is found for r c . If the size of a
perturbation exceeds the value given by r c it is very likely to
survive leading to a deviation from the ball shaped morphol-
ogy of the initially formed grains. It can be assumed that
void formation occurs if the density of nuclei is such that the
average distance between them is larger than r c . Thus, ad-
jacent grains may merge only partially enclosing a volume,
TABLE I. Data used to calculate ( ⳵ r/ ⳵ t) s and ( ⳵ r/ ⳵ t) g .
D g 共m2/s兲 D s 共m2/s兲 ␥ 共J/m2)
⫺4 ⫺14
10 10
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Kröger et al. 1871
FIG. 10. Plot of r⫽ ␴ ⫺1/2 indicating the obtained values of nucleation den-
sities for CVD Cu on PVD Ta and CVD TiN.
which is cutoff the precursor supply and by that forming a
void. From ␴ c ⫽r ⫺2
c a critical nucleation density can be de-
termined using Eq. 共10兲
冉 冊
1/2
共8兲 k BT
␴ c⫽ R. 共11兲
c 0 V 20 ␥ ␦ D g D s
It can be seen that ␴ c is essentially proportional to the
growth rate. For ␴ c a critical value for the nucleation density
of about 5⫻1013 m⫺2 共for r c ⫽150 nm) is calculated. This
value depends mainly on surface self-diffusion of Cu, gas
phase diffusion of the precursor and deposition rate. In Fig.
10 a plot of r⫽ ␴ ⫺1/2 is displayed and the respective experi-
共9兲
mental values for the CVD Cu nucleation densities on PVD
Ta and CVD TiN are indicated by arrows. Since the mea-
sured nucleation density on Ta is about 1013 m⫺2, it is five
times lower than ␴ c resulting in a significant void formation.
On the other hand, the observed nucleation density on CVD
TiN is more than an order of magnitude higher than ␴ c and
thus, no voiding occurs here. It should be mentioned that it is
not unlikely that this explanation holds also, at least partially,
for other polycrystalline thin film systems where void forma-
tion is observed, for example in CVD Al deposition.14
IV. CONCLUSIONS
The influence of kinetics on the nucleation and void for-
mation in copper deposited by CVD was studied by means of
HRSEM, TEM, and AFM. Two different barrier materials
were used as substrate for the CVD Cu deposition: PVD Ta
and CVD TiN. TiN showed a two orders of magnitude
higher sticking coefficient than PVD Ta, leading to a signifi-
cant difference in nucleation density. The higher nucleation
density on CVD TiN resulted in a smoother surface of the Cu
␦ 共Å兲 R 共nm/s兲 V 0 (Å 3 ) c 0 (1/m3) T (K)
20
1 3 1 11.6 10 453
1872 J. Appl. Phys., Vol. 88, No. 4, 15 August 2000 Kröger et al.

films and enabled the deposition of void free films. The Cu
films deposited on Ta showed a high density of voids. A
simple model was developed to understand the dependence
of void formation on the nucleation density. A comparison of
model calculations and experimental findings shows that a
critical nucleation density exists. If the distance between the
grains is too large 共or the nucleation density too low兲 pertur-
bations are formed on the surfaces of the grains leading to
void formation upon merging.
ACKNOWLEDGMENT
R.K. acknowledges a personal grant by the German-
Israeli Minerva Fellowship Foundation.
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