HOT FILAMENT ASSISTED CVD OF TITANIUM NITRIDE FILMS

SADANAND V. DESHPANDE AND ERDOGAN GULARI

Department of Chemical Engineering
University of Michigan, Ann Arbor, MI 48109.

ABSTRACT
Titanium nitride thin films have been deposited using a novel Hot Filament Chemical
Vapor Deposition (HFCVD) technique. In this technique, a resistively heated tungsten wire
(-17000 C) is used to decompose ammonia to obtain highly reactive nitrogen precursor
species. This approach allows for low temperature deposition of nitride thin films. In the
past, we have used this method to deposit good quality silicon and aluminum nitride films.
Titanium nitride thin films have been deposited on Si(100) at substrate temperatures from
500 0 C to 6000C. These films were characterized using X-ray photoelectron spectroscopy
(XPS), X-ray diffraction, Rutherford backscattering spectroscopy (RBS) and scanning
electron microscopy. The effects of deposition pressure, substrate temperature and titanium
chloride flow rate on film properties have been studied. TiN films with resistivities as low as
80.0 gQ-cm have been deposited. RBS analysis indicates that the films serve as excellent
diffusion barriers for copper and aluminum metallization on silicon.
INTRODUCTION
Titanium mononitride (TiN) in thin film form is a good candidate for application in
ultra large scale integrated (ULSI) circuits as a diffusion barrier, adhesion layer for tungsten
deposition and local interconnects [1,2]. It is a refractory nitride (MP - 2950 0 C) with good
thermal and chemical stability, high electrical conductivity, good corrosion and wear
resistance and high hardness. In addition, it adheres well to silicon as well as SiO 2 and has
very low diffusivities for silicon and metals such as platinum, gold, aluminum and copper. As
the device geometries shrink to sub-micron levels and junction depths become shallower,
there is an increased need for a barrier layer to avoid junction spiking. Also with the advent
of multilevel metallization schemes, conformal "glue" layers (or nucleation layers) are
required for interlevel metal deposition and via plug fills [3]. Furthermore, with a drive
toward the use of copper as a replacement for aluminum in advanced circuits, barrier layers
will be needed to avoid copper diffusion [4,5].
Various deposition methods have been utilized to obtain stoichiometric (Ti/N=I.0)
titanium nitride films. These include reactive evaporation followed by rapid thermal
annealing, reactive sputtering, laser physical vapor deposition, ion assisted deposition, and
chemical vapor deposition. Reactive sputtering is currently the most widely used method as it
offers a compromise between reasonably low deposition temperature and satisfactory step
coverage. Also with sputtering, a thin titanium contact layer can be deposited, before
depositing TiN, so as to form a titanium silicide (to reduce contact resistance) upon
subsequent annealing. Chemical vapor deposition, however, holds more promise for future
generations of ULSI circuits due to the stringent need for conformal coverage over high
aspect ratio contact holes and vias.
Hot filament assisted chemical vapor deposition (HFCVD) is a novel approach to
depositing nitride thin films. In the past, we have demonstrated that this method can be used
to obtain high quality silicon and aluminum nitride films at low deposition temperatures [6,7].
In the HFCVD method, a hot metal wire is employed to decompose the precursor gases in
order to obtain highly reactive intermediates necessary for deposition of films at low substrate
temperatures. This paper discusses the application of HFCVD method for depositing titanium
nitride thin films using titanium tetrachloride and ammonia as reactants. Various deposition

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Mat. Res. Soc. Symp. Proc. Vol. 327. ©1994 Materials Research Society
parameters including flow rate, substrate temperature and deposition pressure have been
studied. The films have been characterized using several techniques and the barrier properties
of TiN for aluminum and copper are reported.
EXPERIMENTAL DETAILS
The deposition system used in this study was the same as reported previously [6,7].
Briefly, the reactor consists of a cold-wall, six-inch, six-way stainless steel chamber capable
of processing single 2-inch wafers. The reactor pressure was measured with a capacitance
manometer and controlled by an exhaust throttle valve. Gases were fed into the reactor via
two inlets: one to feed ammonia which flowed over the filament and the other was a gas
dispersal ring that bypassed the hot filament to deliver titanium tetrachloride (TiC14 ) with
carrier gas (and an additional diluent gas). TiCI 4 was introduced into the reactor by helium
carrier gas flowing through a bubbler maintained at 270 C (300K). The pressure above the
bubbler was controlled to obtain the desired titanium chloride flow rate. The titanium source
lines were heated to 40 0 C in order to avoid any vapor condensation. The gas dispersal ring
was held about 2 cm from the susceptor to minimize any complex forming gas phase
reactions between ammonia and titanium chloride. This reactor configuration also allows for
a fine control over the film composition due to the proximity of the gas ring and the susceptor.
The substrates were clamped to a stainless steel susceptor that was heated by two cartridge
heaters. The substrate temperature was monitored using a type C thermocouple clamped to
the susceptor surface close to the substrate. The filament was a resistively heated tungsten
wire (dia-0.25 mm) placed 4 cm away from the substrate. The filament temperature was
measured with an optical pyrometer through a quartz viewport on the reactor. The filament
temperature was kept at 17000C throughout all the runs reported in this study. The deposition
parameters used in this study are summarized below in Table I.

Table I. Deposition parameters for Titanium Nitride (TiN) thin films

Parameter Set point(s)

Reactor pressure 200-500 mTorr
Substrate temperature 500-600 oC
Tungsten filament temperature 1700 oC
Ammonia Flow rate 80.0 sccm
Diluent flow rate (H2) 230.0 sccm
Carrier gas flow rate (He) 30.0 sccm
TiC14 flow rate 0.5-2.0 sccm

The film properties were characterized by various techniques including X-ray

diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, four-point
probe, and Rutherford backscattering measurements. The phase of titanium nitride present in
the films was identified with low angle (3.0 degree) X-ray diffraction measurements. XPS
was used to obtain the film composition in most cases. The film thickness was estimated
2
from cross sectional scanning electron micrographs and RBS measurements (2.0 MeV He +
beam line). The sheet resistivities were measured with a standard four-point probe. And
finally, the diffusion barrier properties were studied with RBS for aluminum and copper films

116
on TiN/Si(100) for various annealing temperatures and annealing times. The samples were
annealed in a hot wall quartz furnace maintained under 5.0 torr argon.

RESULTS AND DISCUSSION

X-ray PhotoelectronSpectroscopy and RBS

The Ti 2 P3/2, N Is, 0 Is, Cl 2p peaks were used for determining the composition of
the films. These peaks were referenced to the adventitious carbon on the film surface which
is assigned a binding energy (BE) of 284.6 eV. The films were ion milled with an Ar+ ion
gun (3 keV) to obtain a compositional depth profile. The surface of the films was always
covered with an oxide due to air exposure upon removal from the deposition chamber. Figure
1 (a), shows changes in the Ti 2p doublet peak as a function of ion milling (sputtering) time.
The surface spectrum corresponds to TiO 2 (Ti4+ oxidation state) with Ti 2 P3/2 peak occurring
at a BE of 458.5 eV. The contribution from TiNx oxidation state is seen as a shoulder in the
Ti 2 P3/2 peak. After 0.2 min. of sputtering, there is an intermediate state corresponding to
titanium oxynitride. And finally, after 25 min. of sputtering the Ti 2 P3/2 peak shifts to BE of
455.1 eV, which corresponds to near stoichiometric titanium nitride [8]. As reported by Saha
and Tompkins [9], the N ls peak in our samples also show a small shoulder on the higher
binding energy side corresponding to a surface oxynitride. This shoulder in the N ls peak
disappears upon ion milling. It should to be pointed out that in the films deposited at 6000 C
there was no chlorine detected by XPS whereas there was about 1.5% chlorine as determined
by RBS. Figure 1 (b), shows an RBS spectrum of a 1350 A thick TiN film on Si(100). A
small chlorine peak can be clearly seen in this spectrum. This comparison suggests that there
can be a preferential loss of chlorine due to sputtering in XPS measurements. Therefore one
should be careful in reporting the minimum deposition temperature for removal of chlorine
(as determined by XPS) to acceptably low levels in TiN films obtained from a TiC14 source.

Energy (MeV)
0.7 1.0 1.3 1.6

(a) TiN N Si Ti

,•t = 25.0 min

""= 5.0 min
kt = 0.2 min
WLtt=0.0min CI
TO(b)
475 470 465 460 455 450 200 300 400 500 600 700 800
Binding Energy (eV) Channel Number

Figure 1. (a) Ti 2p doublet changes with sputtering time, (b) RBS spectrum of a TiN film.

117
Effect of Deposition Conditions
Table II summarizes the results from this part of the study. In the first set of runs
(films 1-4), the TiCI4 flow rate was varied by changing the pressure over the source bubbler.
The helium carrier gas flow rate was held constant at 30.0 sccm. It should be mentioned that
changing the TiC14 flow rate has a negligible effect on the overall partial pressures of
ammonia and hydrogen as their flow rates are high. An increase in TiC14 flow rate increases
the film deposition rate and also increases the oxygen content in the films. As the TiCl4 flow
rate is increased, more of the complex forming gas phase reactions occur and consequently
there is loss of nitrogen containing precursors. The excess TiC14 then reacts with the oxygen
present in the reactor ambient and forms titanium oxynitride (TiOxNy) films. As TiOxNy
forms more easily than TiN, the deposition rate increases with increasing TiC14 flow rate.
Furthermore, the color of the films changes from golden yellow (characteristic of TiN) to red-
brown (characteristic of titanium rich oxynitride films) with increasing titanium chloride flow
rate. These results are similar to those reported elsewhere [10].
In the next set of runs (films 2,5,6), the deposition pressure was varied to study its
effect on the film composition. The nitrogen content in the TiN samples could be varied by
changing the deposition pressure between 200 mTorr and 500 mTorr while keeping all the
flow rates constant. All of these films were deposited at a temperature of 6000 C. The film
stoichiometry changes from titanium rich (N/Ti=0.52) at 500 mTorr to nitrogen rich
(N/Ti= 1.2) at 200 mTorr. A decrease in deposition pressure decreases the residence time of
the reactant gases in the chamber, and therefore, decreases the deposition rate. On the other
hand, a decrease in reactor pressure increases the life time of the nitrogen precursor radicals
generated by the hot filament, which consequently increases the nitrogen incorporation in the
films. The film resistivity also decreases with decreasing pressure due to a reduction in
oxygen incorporation and deposition of near stoichiometric films. Films with resistivities as
low as 80 V1Q-cm were obtained.

Table II. Effect of deposition conditions on film properties

Film # Tsub Pdep TiC14 Flow Dep. Rate Resistivity

(oQ (mTorr) (sccm) % Ti %N % Cl (k/min) (ji-M-cm)
1 600 500 0.5 64.3 27.6 1.1 180.0 273.0
2 600 500 0.75 63.5 32.0 1.0 170.0 225.0
3 600 500 1.0 63.7 25.8 1.5 235.0 362.0
4 600 500 2.0 61.2 23.6 1.3 430.0 340.0
5 600 200 0.75 44.0 52.0 - 55.0 80.0
6 600 350 0.75 48.0 48.5 - 107.0 105.0
7 550 350 0.75 45.7 46.0 1.9 128.0 203.0
8 500 350 0.75 37.0 33.4 7.0 225.0 870.0
* Remainder is oxygen.

And finally, the deposition temperature was changed to study the effect on various
film properties (films 6-8). The chlorine and oxygen content, film resistivity, deposition rate,

118
and film texture change with increasing deposition temperature from 500 to 6000 C. As
determined from X-ray diffraction, the film deposited at 600 0 C had larger grains than those
deposited at lower temperatures. Also, the 6000 C sample had a higher fraction of grains
oriented in < 111> direction than the other two temperatures. A strong temperature
dependence of film texture has been previously reported by Buiting and Otterloo [ 10].
It should be pointed out that in spite of the availability of atomic hydrogen from
decomposition of ammonia/hydrogen, the chlorine content in the films could not be reduced
below a few atomic percent. This indicates that the presence of hydrogen does not have an
effect on the decomposition chemistry of titanium chloride and high deposition temperatures
are indeed necessary to reduce chlorine content.
Diffusion BarrierProperties
We have studied the barrier properties of the TiN films, deposited on unpatterned
Si(100) at a substrate temperature of 600 0 C, for aluminum and copper overlayers. Aluminum
film (1800 A) was deposited on to air-exposed TiN films (1350 A) with electron beam
evaporation. DC magnetron sputtering was used to deposit 2000 A of copper on to
TiN/Si(100). The aluminum samples were annealed up to 4.5 hr at temperatures of 5000 C,
5500C and 600 0 C. The copper films were annealed up to 5.5 hr at temperatures of 550 0 C,
6000C and 650 0 C. As shown in Figure 2, the TiN film serves as an excellent diffusion barrier
for aluminum at anneal temperatures up to 6000 C (which is above the Al-Si eutectic of
5770C). Also as illustrated in Figure 3, these films perform well against copper for
temperatures up to 650 0 C. In both cases, there is some silicon diffusion into the TiN film
after 4.5 hr. anneal (as seen from the advancing silicon edge in the RBS spectra). There is no
significant change in the shape of the Ti peak indicating that the integrity of the barrier is
maintained. It should be mentioned that the TiN films were exposed to air before deposition
of aluminum or copper. This could have led to the "stuffing" of the grain boundaries with
oxygen, and therefore, improving diffusion barrier performance.

NN S0•i 3
j
Si To
4-i S01
E

102

10 -•' 0.5hr anneal

1.5 hranneal
0. hr anneal
10 hranea.5hr 105 anneal
5.5 hranneal
200 300 400 500 600 700 800 200 300 400 500 600 700 800 900
Channel Number Channel Number

Figure 2 and 3. Annealing of Al/TiN/Si films at 600 0 C and Cu/TiN/Si films at 650 0 C

Failure of a polycrystalline barrier layer (that is thermodynamically stable) occurs

mainly due to the diffusion of atoms from the overlayer or substrate along the grain

119
boundaries [1]. Our RBS results indicate that TiN films deposited with HFCVD are of high
density and have a small number of fast diffusion paths (grain boundaries) leading to the
silicon substrate. A recent study reported the failure of LPCVD TiN layers after a 1 hr. anneal
for temperatures above 450 0 C for Cu overlayers [11]. These differences may be attributed to
the variations in microstructure of the films. The LPCVD films in their study were oriented
in the <200> direction. It is interesting to note that in their study the reactively sputtered
films were oriented in the <111> direction and showed better barrier properties than the
LPCVD films. In this study, the films deposited at 6000C showed largely <111> orientation
and have shown excellent barrier properties. It may therefore be surmised that TiN films with
<111> orientation show better diffusion barrier properties than other orientations. In any
case, the role of grain structure, film stress and film roughness should also be considered
when evaluating diffusion barrier properties. In another related study [12], diffusion of
silicon into two TiN films with different microstructure was studied using RBS depth
profiling. It was observed that the film deposited with Ar ion-assisted bombardment, which
had fine-grained dense structure, showed lower diffusivity for silicon than the other film (with
columnar grains) deposited without ion-bombardment.

CONCLUSIONS
In this paper, we have extended the novel hot filament CVD approach to the
deposition of titanium nitride thin films. In spite of highly reactive nitrogen precursors
present in the reactor ambient, low temperature deposition was not possible due to the low
reactivity of TiC14 . The problem of low levels of chlorine contamination remains to be
solved. In future studies, organometallic precursors, such as Ti(N-Me 2)4 , should be tested to
see if lower carbon containing films could be obtained with HFCVD. Depending on the
deposition conditions, films with resistivities from 80 to 870 g0t-cm have been obtained. The
deposition pressure has a significant influence on the film stoichiometry (Ti/N ratio). The
substrate temperature has a strong effect on the microstructure. The films obtained at a
substrate temperature of 600 0 C show a preferred <111> texture. The films are of high density
and show excellent barrier properties for copper and aluminum metallization.
ACKNOWLEDGMENTS
The authors wish to acknowledge the National Science Foundation for partial support
of this study. We appreciate the help from Dr. Victor Rotberg of Michigan Ion Beam
Laboratory with RBS analysis.

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