Journal of the Korean Physical Society, Vol. 54, No. 3, March 2009, pp.

10871090

Temperature Dependence of TiCl4 and NH3 Surface Reactions

in Chemical Vapor Deposition Trap Systems
Donghun Jeong, Jinha Hwang and Heeyeop Chae
Department of Chemical Engineering, Sungkyunkwan University, Suwon 440-746

Seungil Lee and Che Hoo Cho

Milaebo Co. Ltd., Hwasung 445-973

(Received 16 June 2008)

The reaction products of TiCl4 and NH3 cause serious damage to pump systems in the TiN
chemical vapor deposition process in microelectronic device manufacturing. To resolve this issue,
various kinds of trap systems have been installed between the CVD process chambers and the
pumps. In this work, the deposition process inside a thermal trap system was characterized and a
reaction kinetic model was suggested. In the kinetic study, the solid reaction product was deposited
at temperatures below 200  C in a thermal trap system with TiCl4 and NH3 . The relative ratio of
Ti, N and Cl was determined as 1.0 : 4.8 : 4.7 on average from an electron dispersion spectroscopy
(EDS) analysis. The reaction kinetics was modeled with a combined model of deposition and
decomposition reactions. The activation energy of the deposition reaction was determined as 9.6
kJ/mol at temperatures below 120  C and the activation energy of the decomposition reaction was
determined as 29.4 kJ/mol from a thermal gravimetric analysis.
PACS numbers: 47.70.-N, 68.55.A, 81.15.-z, 82.33.Ya
Keywords: TiCl4 , NH3 , Reaction byproduct, Reaction kinetics

I. INTRODUCTION Typically less than 5 % of the precursors are reacted

in the process chamber for the TiN layer deposition and
Titanium nitride (TiN) has been popularly used for most of the reactant gases are exhausted without experi-
various applications such as wear-resistant coating lms
of various mechanical tools, solar energy absorbers and
ow into the
transparent heat mirrors [1{4]. In the semiconductor
industry, TiN has been widely used as a diusion bar-
rier layer and as capacitor electrodes due to its excellent
thermal stability, good diusion blocking capability and
relatively low electrical resistivity [5{9]. Physical vapor
deposition (PVD) is relatively a simpler process than
chemical vapor deposition (CVD) for the formation of
encing reactions. The unreacted reactants and the reac-
tion products (TiCl4 , NH3 , N2 , HCl, etc.)
pump through the exhaust line and deposit unwanted
byproducts on the lower temperature surfaces of the
pump and the exhaust lines. The surface temperature
can be considered as the major dierence in the reaction
environment between the process chamber (>600  C)
and the exhaust line (<200  C). The unwanted byprod-
ucts lead to exhaust line blockage, contamination parti-
TiN thin lms for blanket lms [10]. However, as the
aspect ratio is increased in the contact via, CVD shows
good conformality and CVD processes have become an
essential process for barrier metal layer deposition [11{
15]. TiCl4 and NH3 -based CVD TiN processes have been
cle generation and pump damage. Frequent maintenance
is typically required for TiN CVD processes due to the
unwanted deposition in the exhaust line and the pump
systems. To prevent damage of the pump, various types
of trap systems have been installed between CVD cham-
popularly used due to good lm quality and good confor- bers and pumps to trap unwanted reaction byproducts.
mality [4,11,12,16]. The reaction for the TiN deposition
in the process chamber is known to be as follows [17].
6TiCl4 + 8NH3 ! 6TiN + N2 + 24HCl:
Typically, the reaction temperature is higher than 600
 C.
 E-mail: hchae@skku.edu; Fax: +82-31-290-7272
The trap systems can be classied into two groups, cold
traps and hot traps.
In this work, we have focused on the reaction kinetics
(1) inside the thermal trap systems. The detailed kinetics
of the reaction byproducts in the trap systems is hardly
known and guidelines for trap design are not available
at this moment. The dependence of the reaction kinetics
on the temperature in the trap system was investigated
in this work.
-1087-
-1088- Journal of the Korean Physical Society, Vol. 54, No. 3, March 2009

Table 1. Composition of byproducts from the TiCl4 -NH3

reaction at temperatures below 200  C.
Temp.  C Ti (wt%) N (wt%) Cl (wt%)
90 17.24 27.72 55.04
120 15.40 18.20 66.30
160 19.47 26.11 54.43

determined by using a precision scale, Adventurer from

OHAUS, having a readability of 0.001 g.
The thermal decomposition was analyzed using a Seiko
Exstar 6000TM thermo-gravimetric analysis (TGA) sys-
tem. The reaction products on the clips were heated and
the mass change was recorded as a function of temper-
ature. The rate of increase of the temperature was 5
 C /min in a N2 environment. The morphologies of the
Fig. 1. Schematic diagram of (a) the experimental setup
and (b) the trap system.
II. EXPERIMENTS
A schematic diagram of the trap system used in this
work is shown in Figure 1(a). The reaction byproducts
reaction byproducts were also observed by using eld-
emission scanning electron microscopy (FE-SEM: JSM
7000FTM ) and the composition was determined by us-
ing energy-dispersive spectroscopy (EDS). Platinum (Pt)
was sputtered on the samples in a vacuum of 1 mTorr
for 90 sec to make the samples surface conductive before
the SEM analysis. The atomic composition of the ac-
cumulated products was determined based on the EDS
analysis.
were deposited on the surface of the modied MilaeboTM III. RESULTS AND DISCUSSION

3550 VC trap. The commercial stainless-steel trap was

modied so that in-situ temperature measurements and
deposition rate measurements were possible. The inter-
nal structure of the trap system is shown in Figure 1(b).
It was divided into an exterior case and into an interior
case that had vertical and horizontal fans. The tem-
perature of the trap surface was controlled from room
temperature to 700  C by using resistive heaters located
on the top lid. Surface temperatures in the various loca-
tions were determined by using
exible thermocouples. plex [16]. The chemical composition analysis of the sam-
TiCl4 (99.9999 %) was purchased from Union Material
Techr and NH3 was purchased from Matheson Gasr .
The vaporized 60 sccm of TiCl4 and 160 sccm of NH3
were fed through a Horiba StecTM mass
ow controller The reaction in the trap is controlled by various fac-
(MFC) and were mixed with 500 sccm of N2 carrier gas
before they were introduced into the trap. The process-
ow rate
ing pressure of the thermal trap was maintained at 470
ow conductance. In this study, the eects of
mTorr. The surface temperature was varied from 45  C
to 210  C by controlling the heater on the top from 300
 C to 550  C. The 1 cm  1 cm stainless-steel pieces
were clipped on various locations inside the trap for the
sample weight measurements, as shown in Figure 1. The
process was operated for 4 hours (240 min) and the reac-
tion products were deposited on the stainless-steel clips
located at the various locations. The growth rates of
the reaction products were determined by directly mea-
suring the weights of the products and the clips. The
mass of reaction products on a stainless-steel clip was
The chemical composition determined by using EDS is
shown in Table 1. The byproducts were obtained at trap
surface temperatures of 90  C, 120  C and 160  C. The
atomic ratios of Ti : N : Cl were determined to be (a)
Ti : N : Cl = 1.0 : 5.5 : 4.3, (b) Ti : N : Cl = 1.0 : 4.0 :
5.8 and (c) Ti : N : Cl = 1.0 : 4.9 : 4.0. Fowels and Pol-
lard suggested the intermediate existence of TiCl4
4NH3
through thermal decomposition of the TiCl4
8NH3 com-
ples in this work was close to the Fowels' theoretical work
and the reaction products in the trap were considered to
be TiCl4
4NH3 for the modeling.
tors, including the deposition temperatures the reactant
composition, the partial pressures, the total
and the
temperature on the deposition kinetics were investigated.
The dependence of the deposition rate of TiCl4
4NH3
on the surface temperature is shown in Figure 2. The
growth rate increased as the surface temperature was
increased up to 120  C; then, the growth rate dropped
drastically at higher temperatures. From this result, we
concluded that the total growth rate consisted of a de-
position reaction and a decomposition reaction.
We have divided the reaction kinetics into two regions
and assumed that the deposition reaction was dominant
in the low-temperature region, while the decomposition
Temperature Dependence of TiCl4 and NH3 Surface Reactions


{ Donghun Jeong et al. -1089-

Fig. 2. Eect of temperature on the total growth rate of Fig. 4. TGA and dierential TG curve in the temperature
TiCl4
4NH3 . range 120 210  C.

Fig. 5. Arrhenius plot of the decomposition rates for

Fig. 3. Arrhenius plot of the deposition rates for TiCl4
4NH3 in the higher temperature range.
TiCl4
4NH3 in the low temperature range.
lowing simplied reactions:

reaction was dominant in the high-temperature region. Deposition Reaction : TiCl4 (g) + 4NH3 (g)
The activation energy of the deposition rate was deter- k!
1 TiCl
4NH (s);
4 3 (2)
mined from an Arrhenius plot in the low-temperature Decomposition Reaction : TiCl4
4NH3 (s)
region, as shown in Figure 3. From the slope of the Ar- k!
2 TiCl (g) + 4NH (g): (3)
4 3
rhenius plot, the activation energy was determined as 9.6
kJ/mol. The growth rate resulting from this mechanism is given
The decomposition process was conrmed by using in the following kinetic model:
a thermal gravimetric analysis (TGA) in a N2 en-
Rate = k1 CA
vironment. The TGA and the dierential thermo-
gravitational (DTG) curves were obtained in the tem-  kE2 CB  E  (4)
1 2
perature range from 120  C to 210  C as shown in Fig- = k10 exp
RT
CA k20 exp
RT
CB ;
ure 4. About 13 % of the sample's mass was decomposed
and the DTG curve was used to obtain the activation en- where the growth rate is expressed in units of
ergy of the decomposition. Figure 5 shows an Arrhenius g
cm 2 min 1 and the surface temperature T in K . R
plot of the decomposition reaction in the TGA analysis. is the gas constant in units of kJ
mol 1 K 1 . The pa-
The activation energy of the decomposition reaction was rameters determined based on the experimental results
about 29.4 kJ/mol. are shown in Table 2. Figure 6 compares the growth
To model the growth mechanism, we adopted the fol- rate calculated using the equation to the experimental
-1090- Journal of the Korean Physical Society, Vol. 54, No. 3, March 2009

Table 2. Activation energies for the kinetic model in this shown in Figure 7.
work.
Parameters Values Units IV. CONCLUSION

E1 9.64 kJ mol 1
E2 29.41 kJ mol 1 The reaction kinetics in the thermal trap system of
K10 CA 5.15  102 g cm 2 min 1 TiN deposition processes was characterized in this work.
K20 CB 6.07  104 g cm 2 min
Fig. 6. Kinetics modeling and experimental results.
Fig. 7. Surface morphologies of TiCl4
4NH3 reaction prod-
ucts at (a) 90  C, (b) 120  C and (c) 160  C.
growth rate. The calculated growth rate agrees with the
experimental growth rates.
The surface morphologies of the solid product at dif-
ferent surface temperature are shown in Figure 7. At
90  C, the TiCl4
4NH3 was synthesized with a relatively
smooth surface (Figure 7(a)). As the surface temper-
ature was increased, a granular structure appeared, as
1 The reaction product in the trap systems was identied
as TiCl4
4NH3 . The growth rate increased with increas-
ing surface temperatures for temperatures less than 120
 C; then, it decreased at higher surface temperatures.
The thermal gravimetric analysis results showed that the
decomposition reaction was dominant at higher temper-
atures. The reaction mechanism consisted of deposition
and decomposition reactions. The activation energies of
the deposition and the decomposition reactions were 9.6
and 29.4 kJ/mol
K, respectively.
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