Journal of the Korean Physical Society, Vol. 45, No. 4, October 2004, pp.

1069∼1073

Barrier Characteristics of TaN Films Deposited by Using the Remote

Plasma Enhanced Atomic Layer Deposition Method

Ju Youn Kim, Keun Woo Lee, Hee Ok Park, Young Do Kim and Hyeongtag Jeon∗
Division of Materials Science & Engineering, Hanyang University, Seoul 133-791

Yangdo Kim
School of Materials Science and Engineering, Pusan National University, Pusan 609-735

(Received 4 June 2004)

Remote plasma-enhanced atomic-layer deposition with tertbutyllimidotris(diethylamido)tantal-

um as the Ta precursor and NH3 gas or NH3 plasma as the reactant was used to deposit TaN films,
the TaN films deposited at 250 ◦ C showed a lower carbon impurity contents when NH3 plasma
was used as the reactant. The resistivities of the TaN films processed with NH3 gas and NH3
plasma were approximately 3,000 and 1,000 µΩ·cm, respectively. The growth rates of the TaN film
processed with NH3 gas and NH3 plasma were about 1.3 and 1.4 Å per cycle, respectively. The
TaN films showed a relatively smooth interface and amorphous characteristics exhibited excellent
step coverage on 0.25-µm-wide by 2.5-µm-deep contact hole structure. The barrier characteristics
of Cu/TaN/Si samples were observed after annealing at various temperatures, and the TaN films
failed after annealing at 700 ◦ C.

PACS numbers: 81.15.Gh, 85.40.Ls, 85.40.Sz

Keywords: Remote PEALD, TaN, Diffusion barrier

I. INTRODUCTION talline and provide inadequate protection because grain

Aluminum (Al) and its alloys have been widely used
for contact and interconnection materials in ultra-large-
scale integrated (ULSI) circuits. However, the rapid in-
creases in the RC delay time and electromigration have
become the major problems as integrated circuits ad-
vance into deep sub-micron levels [1, 2]. For these rea-
sons, new contact and interconnection materials with a
lower electrical resistivities and superior electromigra-
tion resistances are necessary to replace Al and its al-
loys. Copper (Cu) is now being evaluated and used as a
contact and/or interconnect metal for deep sub-micron
devices due to its low resistivity and superior electromi-
gration resistance [3]. However, Cu is quite mobile in
Si and SiO2 at elevated temperatures, and its presence
in Si creates trap levels in the forbidden band gap that
are deleterious to device operation [4]. Therefore, an ef-
fective diffusion barrier layer is required to prevent Cu
diffusion. Binary transition-metal nitrides, such as TiN,
TaN, and WN, have been widely investigated and used
as diffusion barriers for Cu metallization in ULSI devices
due to its relatively low resistivities, high melting points,
high thermal stabilities and good adhesion characteris-
tics [5,6]. However, most of these barriers are polycrys-
∗ E-mail: hjeon@hanyang.ac.kr
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boundaries may presumably serve as fast diffusion paths
for copper. Among these materials, TaN is one of most
widely investigated barrier layer candidates for copper
due to its high melting temperature and thermal stabil-
ity against Cu [7].
TaN barrier layers are usually deposited by using the
physical vapor deposition (PVD) and the chemical va-
por deposition (CVD) methods [8]. However, as the in-
terconnect line width shrinks continuously to deep sub-
micron dimensions, the conventional PVD and CVD
methods exhibit problems such as poor step coverage
in deep contacts and via trenches due to the shadow-
ing effect, and high impurity contents and high depo-
sition temperatures, respectively. To solve these prob-
lems, many researchers have investigated the potential
application of the atomic layer deposition (ALD) method
for barrier layer deposition [9, 10]. However, this ALD
method with halogen precursors has problems such as
high Cl contamination and slow growth rate [11, 12].
Therefore, the ALD method with metal-organic precur-
sors has been suggested to solve these problems. How-
ever, the diffusion barrier layers deposited using the ALD
method with metal-organic precursors (MOALD) shows
relatively high carbon impurity incorporation and poor
film density [13].
Recently, many studies have suggested the use of a
plasma to improve the film quality and to overcome the
-1070- Journal of the Korean Physical Society, Vol. 45, No. 4, October 2004

problems involved in the conventional ALD method [14– examined using cross-sectional transmission electron mi-
16]. Therefore, we suggest the remote plasma enhanced croscopy (XTEM), and the step coverages of the TaN
ALD (PEALD) method for overcoming the various prob- films were observed using field emission scanning electron
lems related with previous deposition methods [17]. Re- microscope (FESEM). The barrier characteristics of the
mote PEALD is designed for the substrate to be placed TaN layers were investigated by measuring the resistivi-
outside of the plasma region, which should reduce the ties and surface morphologies of the Cu/TaN/Si samples
carbon impurity and underlayer damages. In this paper, after they had been annealed at various temperatures.
we will analyze the characteristics of TaN thin film dif-
fusion barriers deposited by using remote PEALD with
NH3 plasma and compare them to those for films de- III. RESULTS AND DISCUSSION
posited by using ALD method with NH3 gas.
Figures 1(a) and (b) show typical AES depth pro-
files of TaN films deposited with NH3 gas and NH3
II. EXPERIMENT plasma at 250 ◦ C, respectively. The TaN films showed
relatively constant compositional variations with non-
TaN films were grown on boron-doped p-type Si (100) stoichiometric characteristics and low carbon impurity.
substrates with a resistivity of 5 ∼ 10 Ω-cm by using The stoichiometry of Ta and N was approximately 2
remote PEALD with tertbutyllimidotris(diethylamido) to 1. This is probably due to the high reactivity of
tantalum (TBTDET) as the Ta precursor and NH3 gas the reactant which efficiently released aminocompounds
or NH3 plasma as the reactant. The Si substrates were (NHa (C2 H5 )b ) and hydrocarbons (Cn Hm ) after combin-
cleaned by dipping them in a piranha solution (H2 SO4 ing with the reactants. The carbon and the oxygen im-
: H2 O2 = 4 : 1) for 10 minutes and then in a diluted purities in the TaN films deposited by using the conven-
HF solution (HF : H2 O = 1 : 50) for 1 minute to remove tional ALD method with NH3 gas were about 20 and 25
organic and native oxide, respectively. A downstream-
type remote PEALD reactor with a 13.56-MHz RF power
source was used in this study. Process parameters, such
as the reaction time, the gas flow rate, the growth tem-
perature, and the plasma power, were varied to optimize
process conditions. TBTDET was delivered from an ex-
ternal reservoir at 90 ◦ C and was pulsed into the reactor
using an Ar carrier gas with the flow rate of 35 sccm. The
NH3 reactant gas and the NH3 plasma reactant gas flow
rates were fixed at 50 and 400 sccm, respectively. The
total pressure was kept constant at 1 Torr. The flow rate
of the Ar purge gas was fixed at 100 sccm. The chemi-
cal reaction of the TBTDET pulse and the NH3 -gas or
the NH3 -plasma pulse constituted one basic cycle in this
experiment. An Ar-purge gas was introduced for com-
plete separation of the precursor and the reactant gases.
All gas flows were automatically controlled with the aid
of a solenoid valve. The sequential times of the TBT-
DET, the Ar purge, the NH3 -gas or NH3 -plasma, and
the Ar-purge pulses were fixed to be 5 s each, but the
reactant gas process time was 10 s. The TaN films were
deposited at 250 ◦ C, and the plasma power was fixed
at 200 W. To investigate the diffusion barrier character-
istics of TaN, we deposited Cu films with thicknesses of
1000 Å on the TaN/Si samples by using an e-beam evap-
orator. After Cu deposition, the Cu/TaN/Si structures
were heat-treated at various temperatures in intervals of
50 ◦ C for 1 hour in a vacuum furnace.
The resistivities of TaN films were measured using a
four-point probe technique. Auger electron spectroscopy
(AES) and X-ray photoelectron spectroscopy (XPS) were
utilized to analyze the chemical compositions, impurity
contents, and chemical bonding structures. The mi- Fig. 1. Typical AES depth profiles of TaN films deposited
crostructures and the crystallinities of the TaN films were with (a) NH3 gas and (b) NH3 plasma at 250 ◦ C.
Barrier Characteristics of TaN Films Deposited by Using the Remote Plasma Enhanced · · · – Ju Youn Kim et al.
Fig. 2. High-resolution XPS spectra of (a) Ta and (b) N
in TaN films deposited with NH3 gas and NH3 plasma at 250
◦ and Ta4f5/2 . The chemical states of the Ta4f peak in TaN
C.
at.%, respectively. However, the TaN films deposited by
using the remote PEALD method with a NH3 plasma
showed carbon and oxygen impurity contents below 7
and 10 at.%, respectively. Thus, the TaN films deposited
by using the remote PEALD method showed decreased
impurity contents compared to those of TaN films de-
posited by using the conventional ALD. The decreased
impurity contents for remote PEALD are probably due
to the enhanced reactivity of ammonia radicals which ef-
ficiently decompose the diethyl-amino (N(C2 H5 )2 ) and
the tertbutyl (C(CH3 )3 ) ligands in the plasma process
without dissociating the ligands. Especially, activated
ammonia radicals are thought to play a major role in
the plasma process by effectively breaking the bonds be-
tween Ta and ligands.
The resistivity of TaN films is one of the most im-
portant factors for metal diffusion barrier applications.
The resistivities of TaN films processed with NH3 gas
and NH3 plasma were approximately 3,000 and 1,000
µΩ·cm, respectively. These values are lower than those of
TaN films deposited by using the other deposition meth-
ods [18]. The resistivity of TaN films is reported to be
closely related with the impurity content, and the re-
mote PEALD method significantly reduces the impurity
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Fig. 3. Cross-sectional micrographs of the TaN films de-
posited with (a) NH3 gas and (b) NH3 plasma.
content.
To investigate the nitridation effect for TaN film de-
posited with NH3 gas and NH3 plasma at 250 ◦ C, we used
XPS to examine the chemical bonds of the TaN films de-
posited using NH3 gas and NH3 plasma, as shown in Fig.
2. The Ta4f peak of pure Ta shows a doublet of Ta4f7/2
films were mainly TaN and TaOx . The binding energies
of TaN and TaOx in the Ta4f peak were 23.5 and 26.5 eV,
respectively. As Fig. 2(a) shows, the TaN films deposited
with NH3 plasma showed stronger TaN peaks than the
TaN films deposited with NH3 gas. Also, TaN films de-
posited with NH3 gas showed stronger TaOx peaks than
TaN films deposited with NH3 plasma. In the case of
TaN films deposited with NH3 plasma, a TaN peak asso-
ciated with a binding energy of 397.5 eV was observed,
as shown in Fig. 2(b). However, TaN films deposited
with NH3 gas did not show that TaN peak. Also, an N1s
peak with a binding energy of 405 eV was seen in the
spectra for both types of films, which indicates that N
atoms segregate at the interstitial sites in tantalum films
as impurities. Since the TaN films deposited with NH3
gas only showed a peak at 405 eV while those deposited
with NH3 plasma showed peaks at 397.5 and 405 eV, it
is obvious that the nitridation effect for TaN is increased
with NH3 plasma.
To compare the crystallization of the TaN films de-
posited with NH3 gas and NH3 plasma, we used XTEM
to observe their microstructures, as shown in Fig. 3.
The XTEM micrographs of the TaN films showed a rela-
tively smooth interface and amorphous phase. The thick-
nesses of the TaN films deposited using NH3 gas and NH3
plasma for 100 cycles were about 130 and 140 Å, respec-
tively. The growth rates of the TaN films deposited using
-1072- Journal of the Korean Physical Society, Vol. 45, No. 4, October 2004

Fig. 4. Step coverage of TaN films deposited with (a) NH3

gas and (b) NH3 plasma on about 0.25-µm-wide by 2.5-µm-
deep contact holes. Fig. 5. Changes in the surface morphology of the
Cu/TaN/Si samples deposited by ALD with NH3 gas for an-
nealing temperatures of (a) 650 ◦ C and (b) 700 ◦ C.

NH3 gas and NH3 plasma were about 1.3 and 1.4 Å per
cycle, respectively.
Poor step coverage of and inhomogeneous impurity
distribution in TaN films generally change the contact
resistance and cause poor adhesion. Figure 4 shows the
step coverage of TaN films deposited with NH3 gas and
NH3 plasma on contact holes about 0.25-µm-wide and
2.5-µm-deep. The TaN film showed a conformal step cov-
erage on the contact hole, and the thicknesses of the TaN
films deposited by using conventional ALD with NH3 gas
and remote PEALD with NH3 plasma were very uniform
on the bottoms and the sidewalls of the contact holes.
The results for TaN films deposited by using NH3 gas
and NH3 plasma were similar, which means that TaN
growth was controlled by a self-limiting reaction on the
substrate.
To understand the failure mechanism of a TaN film
as a diffusion barrier, we examined the surface morphol-
ogy and sheet resistance. The surface morphologies and
the sheet resistances of Cu/TaN/Si samples deposited
by using the ALD methods both with NH3 gas and with
NH3 plasma as functions of the annealing temperature Fig. 6. Changes in the surface morphology of the
are observed in Figs. 5 and 6. The Rs value did not vary Cu/TaN/Si samples deposited by remote PEALD with NH3
significantly up to an annealing temperature of 650 ◦ C. plasma for annealing temperatures of (a) 650 ◦ C and (b) 700
However, the Rs value suddenly increased at an anneal- ◦
C.
ing temperature of 700 ◦ C. For a precise analysis of the
increased Rs value at an annealing temperature of 700
◦
C, the Cu films were selectively removed in a HNO3 The etch pits appeared at an annealing temperature of
: H2 O = 1 : 10 solution, and the TaN films were re- 700 ◦ C, which indicates that the TaN films as barriers
moved in an NH4 OH : H2 O2 : H2 O = 1 : 2 : 6 solution showed failure characteristic at an annealing tempera-
; then, the Si surface was etched in a (K2 Cr2 O7 : H2 O ture of 700 ◦ C. This observation implies that the barrier
= 1 : 10) : HF = 1 : 1 solution for 5 s. Etch pits were failure temperatures of the TaN films deposited by using
observed by using scanning electron microscopy (SEM). two different deposition methods were the same.
Barrier Characteristics of TaN Films Deposited by Using the Remote Plasma Enhanced · · · – Ju Youn Kim et al.
IV. CONCLUSIONS
TaN films were successfully deposited using a TBT-
DET precursor with NH3 gas or NH3 plasma. The TaN
films deposited using remote PEALD showed much lower
impurity contents than those of the films deposited by
using other methods wiht the same precursor. TaN films
deposited with NH3 plasma showed lower impurity con-
tents and better thin-film uniformity than the films de-
posited with NH3 gas. The resistivities of TaN films
processed with NH3 gas and NH3 plasma were approxi-
mately 3,000 and 1,000 µΩ·cm, respectively. The growth
rates of the TaN films deposited using NH3 gas and NH3
plasma were about 1.3 and 1.4 Å per cycle, respec-
tively. The TaN films showed relatively smooth inter-
faces, amorphous characteristics, conformal step cover-
age. Failure of the barrier characteristics of TaN film
was observed after annealing at 700 ◦ C.
ACKNOWLEDGMENTS
This work was supported by the National Program for
Tera-level Nanodevices of the Ministry of Science and
Technology as one of the 21 century Frontier Programs.
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