U.S. patent number RE35,785 [Application Number 08/570,613] was granted by the patent office on 1998-05-05 for low-pressure chemical vapor deposition process for depositing high-density highly-conformal, titanium nitride films of low bulk resistivity.
This patent grant is currently assigned to Micron Technology, Inc.. Invention is credited to Todd W. Buley, Gurtej S. Sandhu.
United States Patent |
RE35,785 |
Sandhu , et al. |
May 5, 1998 |
Low-pressure chemical vapor deposition process for depositing
high-density highly-conformal, titanium nitride films of low bulk
resistivity
Abstract
A low-pressure chemical vapor deposition process is disclosed
for creating high-density, highly-conformal titanium nitride films
which have very low bulk resistivity, and which provide excellent
step coverage. The process utilizes a metal-organic compound,
tetrakis-dialkylamido-titanium Ti(NR.sub.2).sub.4, as the primary
precursor, in combination with an activated species which attacks
the alkyl-nitrogen bonds of the primary precursor, and which will
convert the displaced alkyl groups into a volatile compound. Any
noble gas, as well as nitrogen or hydrogen, or a mixture of two or
more of the foregoing may be used as a carrier for the precursor.
The activated species, which may include a halogen, NH.sub.3, or
hydrogen radicals, or a combination thereof, are generated in the
absence of the primary precursor, at a location remote from the
deposition chamber. The wafer is heated to a temperature within a
range of 200.degree.-600.degree. C. The primary precursor molecules
and the activated species are mixed, preferably, just prior to
being ducted into the deposition chamber. Relatively uncontaminated
titanium nitride deposits on the heated wafer surface.
Inventors: |
Sandhu; Gurtej S. (Boise,
ID), Buley; Todd W. (Mesa, AZ) |
Assignee: |
Micron Technology, Inc. (Boise,
ID)
|
Family
ID: |
21944822 |
Appl.
No.: |
08/570,613 |
Filed: |
September 21, 1995 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
046685 |
Apr 14, 1993 |
05246881 |
Sep 21, 1993 |
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Current U.S.
Class: |
438/680;
427/255.394; 427/573; 427/96.8; 438/685 |
Current CPC
Class: |
C23C
16/34 (20130101); C23C 16/4482 (20130101); C23C
16/452 (20130101); H01L 21/76843 (20130101) |
Current International
Class: |
C23C
16/34 (20060101); C23C 16/448 (20060101); C23C
16/452 (20060101); H01L 21/70 (20060101); H01L
21/768 (20060101); H01L 021/285 () |
Field of
Search: |
;437/190,192,245,246
;427/99,248.1,255.1,569,573,255.2 ;118/723ME,723ER,723IR
;438/681,685 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Fix, R.M., et al., "Synthesis of Thin Films . . . ," Chem. Mater.,
vol. 2, No. 3, 1990, pp. 235-241. .
Sherman, A., "Growth and Properties of Low Pressure . . . ",
Japanese J. Appl. Phys., vol. 30, No. 12B, Dec. 1991, pp.
3553-3557. .
Sandhu, G.S., et al., "Metalorganic Chemical Vapor Deposition of
TiN . . . ", Appl. Phys. Lett., 62(3), 18 Jan. 1993, pp. 240-242.
.
Intemann, A., et al., "Films Properties of CVD Titanium Nitride . .
. ", J. Electrochem. Soc., vol. 140, No. 11, Nov. 1993, pp.
3215-3222..
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Primary Examiner: Quach; T. N.
Attorney, Agent or Firm: Trask, Britt & Rossa
Claims
We claim:
1. A chemical vapor deposition process for depositing a titanium
nitride film on a substrate, said process comprising the steps
of:
(1) disposing the substrate on a heated susceptor plate within a
chemical vapor deposition chamber;
(2) admitting a mixture of vaporized tetrakis-dialkylamido-titanium
as the primary precursor compound and an activated species into
said chamber, said activated species having been created in a
plasma discharge at a location remote from the chamber, and said
primary precursor compound having not been subjected to a plasma
discharge.
2. The process of claim 1, wherein said precursor compound is
tetrakis-dimethylamido-titanium.
3. The process of claim 1, wherein said activated species reacts
with the alkyl-nitrogen bonds of the primary precursor compound,
and forms a volatile compound with the alkyl groups thereof.
4. The process of claim 3, wherein said substrate is heated by said
susceptor plate to a temperature sufficient to cause remnants of
said vaporized precursor compound to deposit on said substrate in
the form of a titanium nitride film.
5. The process of claim 4, wherein said substrate is heated to a
temperature within a range of 200.degree.-600.degree. C.
6. The process of claim 5, wherein said substrate is heated to a
temperature of about 400.degree. C.
7. The process of claim 3, wherein reaction products are removed
from the chamber as the reaction proceeds.
8. The process of claim 3, wherein the walls of said chamber are
maintained at a temperature that is insufficient to pyrolyze the
primary precursor compound.
9. The process of claim 1, wherein said activated species is a
halogen radical.
10. The process of claim 9, wherein said activated species is a
chlorine radical.
11. The process of claim 9, wherein said activated species is a
fluorine radical.
12. The process of claim 1, wherein said activated species is a
hydrogen radical.
13. The process of claim 1, wherein said activated species is an
NF.sub.3 radical.
14. The process of claim 1, wherein said activated species is a
NH.sub.3 radical.
15. The process of claim 1, wherein said at least one carrier gas
is utilized to transport the vaporized primary precursor compound
into the chamber.
16. The process of claim 15, wherein said carrier gas is selected
from a group consisting of the noble gases, nitrogen and
hydrogen.
17. The process of claim 16, wherein said precursor compound is
introduced into said carrier gas in a bubbler apparatus.
18. A chemical vapor deposition process for depositing a titanium
nitride film on a semiconductor wafer comprising the steps of:
(1) disposing the semiconductor wafer on a heated susceptor plate
within a chemical vapor deposition chamber;
(2) admitting at least one inert carrier gas into said chamber,
said carrier gas being at least partially saturated with a
metal-organic titanium compound as the primary precursor compound;
and
(3) admitting an activated species into said chamber, said
activated species having been created in a plasma discharge at a
location remote from the chamber, and said primary precursor
compound having not been subjected to a plasma discharge.
19. The process of claim 18, wherein said primary precursor
compound is tetrakis-dialkylamido-titanium.
20. The process of claim 19, wherein said activated species reacts
with the alkyl-nitrogen bonds of the primary precursor compound,
and forms a volatile compound with the alkyl groups thereof.
21. The process of claim 18, wherein said semiconductor wafer is
heated by said susceptor plate to a temperature sufficient to cause
remnants of said primary precursor compound to deposit on the
surface of the wafer.
22. The process of claim 18, wherein said at least one carrier gas
is selected from a group consisting of the noble gases, nitrogen
and hydrogen. .Iadd.
23. A chemical vapor deposition process for depositing a titanium
nitride film on a semiconductor wafer comprising the steps of:
disposing the semiconductor wafer on a heated susceptor plate
within a chemical vapor deposition chamber;
admitting into said chamber a metal-organic titanium compound as
the primary precursor compound; and
admitting an activated species into said chamber, said activated
species having been created in a plasma discharge at a location
remote from the chamber, and said primary precursor compound having
not been subjected to a plasma discharge..Iaddend..Iadd.24. The
process of claim 23, wherein said primary precursor compound is
tetrakis-dialkylamido-titanium..Iaddend..Iadd.25. The process of
claim 24, wherein said activated species reacts with the
alkyl-nitrogen bonds of the primary precursor compound, and forms a
volatile compound with the alkyl groups thereof..Iaddend..Iadd.26.
The process of claim 23, wherein said semiconductor wafer is heated
by said susceptor plate to a temperature sufficient to cause
remnants of said primary precursor compound to deposit on the
surface of the wafer..Iaddend..Iadd.27. The process of claim 23,
wherein a carrier gas is also admitted into the
chamber..Iaddend..Iadd.28. The process of claim 27, wherein said
carrier gas is selected from a group consisting of the noble gases,
nitrogen and hydrogen..Iaddend.
Description
FIELD OF THE INVENTION
This invention relates to integrated circuit manufacturing
technology and, more specifically, to processes for depositing
titanium carbonitride films via chemical vapor deposition.
BACKGROUND OF THE INVENTION
The compound titanium nitride (TiN) has numerous potential
applications because it is extremely hard, chemically inert
(although it readily dissolves in hydrofluoric acid), an excellent
conductor, possesses optical characteristics similar to those of
gold, and has a melting point around 3000.degree. C. This durable
material has long been used to gild inexpensive jewelry and other
art objects. However, during the last ten to twelve years,
important uses have been found for TiN in the field of integrated
circuit manufacturing. Not only is TiN unaffected by integrated
circuit processing temperatures and most reagents, it also
functions as an excellent barrier against diffusion of dopants
between semiconductor layers. In addition, TiN also makes excellent
ohmic contact with other conductive layers.
In a common application for integrated circuit manufacture, a
contact opening is etched through an insulative layer down to a
diffusion region to which electrical contact is to be made.
Titanium metal is then sputtered over the wafer so that the exposed
surface of the diffusion region is coated. The titanium metal is
eventually converted to titanium silicide, thus providing an
excellent conductive interface at the surface of the diffusion
region. A titanium nitride barrier layer is then deposited, coating
the walls and floor of the contact opening. Chemical vapor
deposition of tungsten or polysilicon follows. In the case of
tungsten, the titanium nitride layer provides greatly improved
adhesion between the walls of the opening and the tungsten metal.
In the case of the polysilicon, the titanium nitride layer acts as
a barrier against dopant diffusion from the polysilicon layer into
the diffusion region.
At least five techniques are currently available for creating thin
titanium nitride films having low bulk resistivity: reactive
sputtering; annealing of an already deposited titanium layer in a
nitrogen ambient; a high-temperature atmospheric pressure chemical
vapor deposition (APCVD) process, using titanium tetrachloride,
nitrogen and hydrogen as reactants; a low-temperature APCVD
process, using ammonia and Ti(NR.sub.2).sub.4 compounds as
precursors; a LPCVD; and a low-pressure CVD process using ammonia
and Ti(NMe.sub.2).sub.4 as precursors. Each of these four processes
has its associated problems.
Both reactive sputtering and nitrogen ambient annealing of
deposited titanium result in films having poor step coverage, which
are not useable in submicron processes. Chemical vapor deposition
processes have an important advantage in that a conformal layers of
any thickness may be deposited. This is especially advantageous in
ultra-large-scale-integration circuits, where minimum feature
widths may be smaller than 0.5.mu.. Layers as thin as 101/8 may be
readily produced using CVD. However, TiN coatings prepared used the
high-temperature APCVD process must be prepared at temperatures
between 900.degree.-1000.degree. C. The high temperatures involved
in this process are incompatible with conventional integrated
circuit manufacturing processes. Hence, depositions using the APCVD
process are restricted to refractory substrates such as tungsten
carbide. The low-temperature APCVD, on the other hand, though
performed within a temperature range of 100.degree.-400.degree. C.
that is compatible with conventional integrated circuit
manufacturing processes, is problematic because the precursor
compounds (ammonia and Ti(NR.sub.2).sub.4) react spontaneously in
the gas phase. Consequently, special precursor delivery systems are
required to keep the gases separated during delivery to the
reaction chamber. In spite of special delivery systems, the highly
spontaneous reaction makes full wafer coverage difficult to
achieve. Even when achieved, the deposited films tend to lack
uniform conformality, are generally characterized by poor step
coverage, and tend to deposit on every surface within the reaction
chamber, leading to particle problems. Finally, the low-pressure
CVD process, though producing layers of uniform thickness, does not
provide acceptable step coverage for high aspect ratio
trenches.
SUMMARY OF THE INVENTION
This invention is a process for depositing high-density,
highly-conformal titanium nitride films which have very low bulk
resistivity and excellent step coverage. The deposition process
takes place in a low-pressure chamber (i.e, a chamber in which
pressure has been reduced to between 0.1 and 100 Torr prior to
deposition), and utilizes a metal-organic compound,
tetrakis-dialkylamido-titanium Ti(NR.sub.2).sub.4, as the primary
precursor in combination with an activated species which attacks
the alkyl-nitrogen bonds of the primary precursor, and which will
convert the displaced alkyl groups into a volatile compound. Any
noble gas, as well as nitrogen or hydrogen, or a mixture of two or
more of the foregoing may be used as a carrier for the precursor.
The activated species, which may include halogen, NH.sub.3, or
hydrogen radicals, or a combination thereof, are generated in the
absence of the primary precursor, at a location remote from the
deposition chamber. Remote generation of the activated species is
required because it is not desirable to employ a plasma CVD
process, as Ti(NR.sub.2).sub.4 is known to break down in plasma,
resulting in large amounts of carbon in the deposited film. A high
carbon content will elevate the bulk resistivity of the film to
levels that are unacceptable for most integrated circuit
applications. The wafer is heated to a temperature within a range
of 200.degree.-600.degree. C. The primary precursor molecules and
the activated species are mixed, preferably, just prior to being
ducted into the deposition chamber. It is hypothesized that as soon
as the mixing has occurred, the activated species begin to tear
away the alkyl groups from the primary precursor molecules.
Relatively uncontaminated titanium nitride deposits on the heated
wafer surface.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a block schematic diagram of the low-pressure chemical
vapor deposition reactor system and the remote plasma generation
equipment used for the subject process.
PREFERRED EMBODIMENT OF THE INVENTION
The new process for depositing high-density, highly-conformal
titanium nitride films which have very low bulk resistivity and
excellent step coverage, will be described in reference to the
low-pressure chemical vapor deposition reactor system depicted in
FIG. 1. The deposition process takes place in a cold wall chamber
11 in which pressure has been reduced to between 0.1 and 100 torr.
A pressure of 0.5 torr is deemed to be optimum. A wafer 12, on
which the deposition will be performed, is mounted on a susceptor
13, which is heated to a temperature within a range of
200.degree.-600.degree. C. by a heat lamp array 14. A wafer
temperature of about 400.degree. C. is deemed to be optimum for
integrated circuit manufacture. A carrier gas selected from a group
consisting of the noble gases and nitrogen and hydrogen is bubbled
through liquid tetrakis-dialkylamido-titanium 15, the primary
precursor compound, in a bubbler apparatus 16. A carrier gas flow
rate of 100 scc/min. was maintained through the bubbler apparatus
16 during the deposition process, and the primary precursor
compound 15 was maintained at a constant temperature of
approximately 40.degree. C. Other techniques for vaporizing a
semivolatile compound are also known in the art and may be used in
place of the bubbler apparatus.
Tetrakis-dialkylamido-titanium, or Ti(R.sub.2).sub.4, molecularly
consists of a titanium atom to which four nitrogen atoms are single
bonded, with each nitrogen atom also being single bonded to a pair
of alkyl groups. It should be noted that
tetrakis-dialkylamido-titanium is a family of compounds, of which
tetrakis-dimethylamido-titanium, tetrakis-diethylamido-titanium and
tetrakis-dibutylamido-titanium has been synthesized. Because of its
lower carbon content per unit of molecular weight, the first
compound is preferred because there is less carbon available to be
incorporated as an impurity into the film. Nevertheless, any of the
three compounds or any combination of the three compounds are
deemed to be operative for the present invention.
Referring once again to FIG. 1, the carrier gas, at least partially
saturated with vaporized primary precursor compound 15, is
transported via a primary intake manifold 17A to a premix chamber
20. A secondary precursor compound is introduced into a secondary
intake manifold 17B. The secondary precursor compound passes
between a pair of plates 19 to which a radio frequency (RF) voltage
is applied by RF generator 18. The portion of the secondary intake
manifold 17B passing between plates 19 is constructed from quartz
in order to permit the effect of the RF field to be exerted
Referring once again to FIG. 1, the mixture of primary precursor
compound, activated secondary precursor compound, and carrier gas
is ducted from premix chamber 20 to a shower head 21, from which
they enter the chamber 11. Relatively uncontaminated titanium
nitride deposits on the surface of the heated wafer 12. Reaction
products and carrier gas are withdrawn from the chamber 11 via an
exhaust manifold 22. Incorporated in the exhaust manifold 22 are a
pressure sensor 23, a pressure switch 24, a vacuum valve 25, a
pressure control valve 26, a blower 27, and a particulate filter,
which filters out solid reactants before the exhaust is vented to
the atmosphere. During the deposition process, the pressure within
chamber 11 is maintained within a pressure of preferably, but not
limited to, 0.1 to 100 torr by pressure control components 23, 24,
25, 26, and 27.
Experiments have been performed using both Cl.sub.2 and NF.sub.3 as
secondary precursor compounds. A control process was run in which
the primary precursor compound was pyrolized in the absence of a
secondary precursor compound (activated or unactivated). The
following chart provides bulk resistivity values for films having a
thickness of about 1501/8 deposited using the various
processes.
______________________________________ Resistivity Process (in
.mu.ohm-cm) ______________________________________ Control 16,800
Cl.sub.2 4,500 NF.sub.3 2,000 NH.sub.3 1,700
______________________________________
Conformality of the titanium nitride films deposited by the subject
process has been experimentally observed to be therein. A plasma
discharge is struck and maintained as the secondary precursor
compound passes through the quartz portion of the secondary
manifold between the plates 19, resulting in activated species. The
secondary precursor compound, containing activated species, is
ducted into premix chamber 20, where it is mixed with the vaporized
primary precursor compound 15 and the carrier gas.
The secondary precursor compound is chosen, such that when
activated by the RF voltage, activated species result which attack
the alkyl-nitrogen bonds of the primary precursor compound, and
which will convert the displaced alkyl groups into a volatile
compound. The activated species, which may include halogen,
NH.sub.3, or hydrogen radicals, or a combination thereof, must be
generated in the absence of the primary precursor compound, at a
location remote from the deposition chamber. Remote generation of
the activated species is essential because it is not desirable to
employ a plasma CVD process, as Ti(NR.sub.2).sub.4 is known to
break down in plasma, resulting in large amounts of carbon in the
deposited film. A high carbon content will elevate the bulk
resistivity of the film to levels that are unacceptable for most
integrated circuit applications. It is hypothesized that as soon as
the mixing of the activated species and the primary precursor
compound has occurred, the activated species begin to tear away the
alkyl groups from the primary precursor molecules. Thus, the
primary precursor molecules and the activated species are mixed,
preferably, just prior to being ducted into the deposition chamber.
within a range of 5% of the average thickness.
For the films deposited by the subject process, film thickness step
coverage on vertical wall portions near the base of 0.5.mu.-wide,
2.5.mu.-deep contact openings is greater than 90 percent of the
horizontal film thickness near the top of the openings.
Although only a single embodiment of the inventive process has been
disclosed herein, it will be obvious to those having ordinary skill
in the art that modifications and changes may be made thereto
without affecting the scope and spirit of the invention as claimed.
For example, other metal-organic titanium compounds which have
bonds with reactivities similar to those of
tetrakis-dialkylamido-titanium will likely react in a similar
manner and with similar results. It is also to be understood that
the process parameters disclosed herein are meant to be
illustrative, and are not meant to be limiting. In addition, it
should be understood that titanium nitride may be deposited on
substrates other than a semiconductor wafers using the subject
process.
* * * * *