U.S. patent application number 14/183301 was filed with the patent office on 2014-06-12 for method of manufacturing semiconductor device and substrate processing apparatus.
This patent application is currently assigned to Hitachi Kokusai Electric Inc.. The applicant listed for this patent is Hitachi Kokusai Electric Inc.. Invention is credited to Yukinao KAGA, Tatsuyuki SAITO, Masanori SAKAI, Takashi YOKOGAWA.
Application Number | 20140162454 14/183301 |
Document ID | / |
Family ID | 44309276 |
Filed Date | 2014-06-12 |
United States Patent
Application |
20140162454 |
Kind Code |
A1 |
KAGA; Yukinao ; et
al. |
June 12, 2014 |
METHOD OF MANUFACTURING SEMICONDUCTOR DEVICE AND SUBSTRATE
PROCESSING APPARATUS
Abstract
Provided is a method of manufacturing a semiconductor device.
The method includes (a) loading a substrate into a processing
chamber; (b) starting a supply of a first processing gas into the
processing chamber; (c) starting a supply of a second processing
gas into the processing chamber during the supply of the first
processing gas; (d) stopping the supply of the second processing
gas during the supply of the first processing gas; (e) stopping the
supply of the first processing gas after performing the step (d);
(f) removing the first processing gas and the second processing gas
remaining after performing the step (e) from the processing
chamber; and (g) unloading the substrate from the processing
chamber.
Inventors: |
KAGA; Yukinao; (Toyama,
JP) ; SAITO; Tatsuyuki; (Toyama, JP) ; SAKAI;
Masanori; (Toyama, JP) ; YOKOGAWA; Takashi;
(Toyama, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Hitachi Kokusai Electric Inc. |
Tokyo |
|
JP |
|
|
Assignee: |
Hitachi Kokusai Electric
Inc.
Tokyo
JP
|
Family ID: |
44309276 |
Appl. No.: |
14/183301 |
Filed: |
February 18, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13012320 |
Jan 24, 2011 |
8691708 |
|
|
14183301 |
|
|
|
|
Current U.S.
Class: |
438/680 |
Current CPC
Class: |
H01L 21/32051 20130101;
H01L 21/28556 20130101; C23C 16/45574 20130101; H01L 21/28562
20130101; C23C 16/45523 20130101; C23C 16/34 20130101 |
Class at
Publication: |
438/680 |
International
Class: |
H01L 21/3205 20060101
H01L021/3205 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 25, 2010 |
JP |
2010-013014 |
Nov 30, 2010 |
JP |
2010-266422 |
Claims
1. A method of manufacturing a semiconductor device, comprising:
(a) loading a substrate into a processing chamber; (b) starting a
supply of a first processing gas into the processing chamber; (c)
starting a supply of a second processing gas into the processing
chamber during the supply of the first processing gas; (d) stopping
the supply of the second processing gas during the supply of the
first processing gas; (e) stopping the supply of the first
processing gas after performing the step (d); (f) removing the
first processing gas and the second processing gas remaining after
performing the step (e) from the processing chamber; and (g)
unloading the substrate from the processing chamber.
2. The method according to claim 1, wherein the steps (b) through
(f) are performed in order a predetermined number of times to form
a predetermined film.
3. The method according to claim 1, wherein the first processing
gas includes a nitrogen-containing gas, the second processing gas
includes a titanium-containing gas, and the film formed on the
substrate includes a titanium nitride.
4. The method according to claim 1, wherein the second processing
gas includes a metal-containing gas.
5. The method according to claim 1, wherein a time period during
which the first processing gas is supplied between the steps (b)
and (c) ranges from 0.1 to 30 seconds.
6. The method according to claim 1, wherein a time period during
which the first processing gas is supplied between the steps (d)
and (e) ranges from 0.1 to 30 seconds.
7. The method according to claim 1, further comprising: (h)
starting a supply of the first processing gas into the processing
chamber after performing the step (f) and stopping the supply of
the first processing gas; and (i) removing the first processing gas
remaining after performing the step (h) from the processing
chamber.
8. The method according to claim 7, wherein the steps (b) through
(i) are performed in order a predetermined number of times to form
a predetermined film.
9. The method according to claim 7, wherein the first processing
gas includes a nitrogen-containing gas, the second processing gas
includes a titanium-containing gas, and the film formed on the
substrate includes a titanium nitride.
10. The method according to claim 7, wherein the second processing
gas includes a metal-containing gas.
Description
CROSS-REFERENCE TO RELATED PATENT APPLICATION
[0001] This U.S. non-provisional patent application is continuation
application of U.S. patent application Ser. No. 13/012,320 filed on
Jan. 24, 2011 and claims priority under 35 U.S.C. .sctn.119 of
Japanese Patent Application Nos. 2010-013014 and 2010-266422 filed
on Jan. 25, 2010 and Nov. 30, 2010, respectively, in the Japanese
Patent Office, the entire contents of which are hereby incorporated
by reference.
1. FIELD OF THE INVENTION
[0002] The present invention relates to a method of manufacturing a
semiconductor device and a substrate processing apparatus, and more
particularly, to a method of manufacturing a semiconductor device
and a substrate processing apparatus wherein a metal film or a
metal compound is formed on a substrate (a wafer) using a
halogenated metal compound or an organometallic compound as a
source.
2. DESCRIPTION OF THE RELATED ART
[0003] Methods of forming a predetermined film on a substrate
include a chemical vapor deposition (CVD) method. The CVD method is
a method of forming a film including elements included in source
molecules as components on a substrate using a reaction of at least
two sources in a gas phase or on a surface of the substrate. In
addition, the CVD method includes an atomic layer deposition (ALD)
method. The ALD method includes alternatively supplying at least
two sources used for forming a film onto a substrate under
predetermined film-forming conditions (temperature, time, etc), and
adsorbing the sources in a unit of an atomic layer wherein the
formation is controlled at an atomic layer level using a surface
reaction. The substrate may be processed at a lower substrate
temperature (processing temperature) compared to the conventional
CVD method, and a thickness of a film to be formed may be
controlled by the number of film-forming cycles. In addition, a
titanium nitride (TiN) film as disclosed in Patent Document 1 may
be, for example, used as a conductive film formed on the substrate.
In addition, tantalum (Ta), aluminum (Al), tungsten (W), manganese
(Mn) and nitrides thereof, titanium (Ti), etc. may be used as the
conductive film. In addition, oxides and nitrides of hafnium (Hf),
zirconium (Zr), Al, etc. may be, for example, used as an insulating
film.
PRIOR-ART DOCUMENT
Patent Document
[0004] [Patent Document 1] International Publication No.:
2007/020874
[0005] When the titanium nitride (TiN) film is formed on the
substrate to be processed as the conductive film, a titanium
tetrachloride (TiCl.sub.4), for example, may be used as a
Ti-containing source, and an ammonia (NH.sub.3) may be used as a
nitriding gas. A TiN continuous film generally shows a columnar
structure, but when the TiN film is formed using only the CVD
method, the TiN continuous film tends to grow randomly from the
beginning to the end of the film formation compared to the ALD
method, resulting in coarse crystal grains or a rough film surface.
As a ratio of air gap in the film increases, the film density may
be reduced, resulting in an increase in resistivity. Moreover, a
concentration of a chlorine (Cl) in the film may be increased, the
resistivity of a TiN film itself may be increased, or a gas may be
discharged in a subsequent process after the formation of the TiN
film, etc.
[0006] Particularly, it is known that, when a film-forming
temperature is reduced to 300.degree. C., a film grows in a
thorn-like shape, and its properties such as a surface roughness
and a film density may be significantly degraded.
[0007] Meanwhile, the TiN continuous film formed by the ALD method
may have a smooth surface compared to the films formed by the CVD
method, thereby obtaining the TiN film having a relatively low
resistance. In addition, it is possible to ensure a good step
coverage. On the other hand, since a film-forming speed is slow
compared to the CVD method, it takes longer to obtain a film having
a desired thickness, and a thermal budget of a substrate may be
increased.
SUMMARY OF THE INVENTION
[0008] Therefore, it is an object of the present invention to solve
above-described problems, and provide a method of manufacturing a
semiconductor device and a substrate processing apparatus capable
of providing a TiN film that is higher in quality than a TiN film
formed by the conventional CVD method, at a higher film-forming
speed, that is, with a higher productivity than the TiN film formed
by the ALD method.
[0009] In order to solve the above problems, according to one
embodiment of the present invention, there is provided a method of
manufacturing a semiconductor device, including: (a) loading a
substrate into a processing chamber; (b) starting a supply of a
first processing gas into the processing chamber; (c) starting a
supply of a second processing gas into the processing chamber
during the supply of the first processing gas; (d) stopping the
supply of the second processing gas during the supply of the first
processing gas; (e) stopping the supply of the first processing gas
after performing the step (d); (f) removing the first processing
gas and the second processing gas remaining after performing the
step (e) from the processing chamber; and (g) unloading the
substrate from the processing chamber.
[0010] According to another embodiment of the present invention,
there is provided a method of manufacturing a semiconductor device,
including: (a) loading a substrate into a processing chamber; (b)
forming a predetermined film on the substrate by simultaneously
supplying the first processing gas and the second processing gas in
the processing chamber; (c) stopping the supply of the first
processing gas and the second processing gas and removing the first
processing gas and the second processing gas remaining in the
processing chamber; (d) modifying the film formed on the substrate
by supplying the second processing gas into the processing chamber;
(e) adsorbing at least a portion of the second processing gas onto
the substrate by stopping the supply of the second processing gas
and supplying the first processing gas into the processing chamber;
and (f) unloading the substrate from the processing chamber.
[0011] According to still another embodiment of the present
invention, there is provided a method of manufacturing a
semiconductor device, including: (a) loading a substrate into a
processing chamber; (b) adsorbing a first element onto the
substrate by supplying the first processing gas containing the
first element into the processing chamber; (c) forming a
predetermined film on the substrate by supplying the second
processing gas containing a second element while supplying the
first processing gas into the processing chamber such that the
second processing gas reacts with the first processing gas and the
first element adsorbed onto the substrate; (d) modifying the film
formed on the substrate by stopping the supply of the first
processing gas and supplying the second processing gas into the
processing chamber; (e) stopping the supply of the second
processing gas and removing the first processing gas and the second
processing gas remaining in the processing chamber; and (f)
unloading the substrate from the processing chamber, wherein the
steps (b) through (e) are performed in order repeatedly a
predetermined number of times.
[0012] According to yet another embodiment of the present
invention, there is provided a method of manufacturing a
semiconductor device, including: (a) loading a substrate into a
processing chamber; (b) supplying the first processing gas into the
processing chamber; (c) supplying the second processing gas into
the processing chamber while supplying the first processing gas
into the processing chamber; (d) stopping the supply of the first
processing gas and supplying the second processing gas; (e)
stopping the supply of the second processing gas and removing the
first processing gas and the second processing gas remaining in the
processing chamber; and (f) unloading the substrate from the
processing chamber, wherein the steps (a) through (f) are performed
in order repeatedly a predetermined number of times.
[0013] According to yet another embodiment of the present
invention, there is provided a substrate processing apparatus
including: a processing chamber for accommodating a substrate; a
first processing gas supply means for supplying the first
processing gas into the processing chamber; a second processing gas
supply means for supplying the second processing gas into the
processing chamber; an exhaust means for exhausting an inside of
the processing chamber; and a control unit for controlling the
first processing gas supply means, the second processing gas supply
means, and the exhaust means to form a film on the substrate by
simultaneously supplying the first processing gas and the second
processing gas into the processing chamber, stopping the supply of
the first processing gas and the second processing gas and
exhausting the first processing gas and the second processing gas
remaining in the processing chamber, and modifying the film formed
on the substrate by supplying the second processing gas into the
processing chamber, wherein, when the first processing gas and the
second processing gas are simultaneously supplied into the
processing chamber, the control unit controls the first processing
gas supply means and the second processing gas supply means in a
manner that a time period for supplying the second processing gas
into the processing chamber is longer than a time period for
supplying the first processing gas into the processing chamber.
[0014] According to the present invention, it is possible to
provide a TiN film that is higher in quality than the TiN film
formed by the conventional CVD method, at the higher film-forming
rate, that is, with the higher productivity than the TiN film
formed by the ALD method.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a perspective view schematically illustrating a
schematic configuration of a substrate processing apparatus
preferably used in one embodiment of the present invention.
[0016] FIG. 2 is a configuration diagram schematically exemplifying
a processing furnace and accompanying members thereof preferably
used in one embodiment of the present invention, particularly a
longitudinal cross-sectional view illustrating a part of the
processing furnace.
[0017] FIG. 3 is a cross-sectional view of the processing furnace
shown in FIG. 2 taken along line A-A preferably used in one
embodiment of the present invention.
[0018] FIG. 4 is a diagram illustrating a film-forming sequence in
accordance with a first embodiment of the present invention.
[0019] FIG. 5 is a flow diagram illustrating a process in
accordance with a first embodiment of the present invention.
[0020] FIG. 6 is a diagram illustrating a film-forming sequence in
accordance with a second embodiment of the present invention.
[0021] FIG. 7 is a flow diagram illustrating a process in
accordance with a second embodiment of the present invention.
[0022] FIG. 8 is a diagram illustrating a film-forming sequence in
accordance with a third embodiment of the present invention.
[0023] FIG. 9 is a flow diagram illustrating a process in
accordance with a third embodiment of the present invention.
[0024] FIG. 10 is a diagram illustrating a film-forming sequence in
accordance with a fourth embodiment of the present invention.
[0025] FIG. 11 is a flow diagram illustrating a process in
accordance with a fourth embodiment of the present invention.
[0026] FIG. 12 is a diagram illustrating a film-forming sequence in
accordance with a fifth embodiment of the present invention.
[0027] FIG. 13 is a flow diagram illustrating a process in
accordance with a fifth embodiment of the present invention.
[0028] FIG. 14 is a diagram illustrating a film-forming sequence in
accordance with a sixth embodiment of the present invention.
[0029] FIG. 15 is a flow diagram illustrating a process in
accordance with a sixth embodiment of the present invention.
[0030] FIG. 16 is a diagram illustrating a film-forming sequence in
accordance with a seventh embodiment of the present invention.
[0031] FIG. 17 is a flow diagram illustrating a process in
accordance with a seventh embodiment of the present invention.
[0032] FIG. 18 is a diagram illustrating a film-forming sequence in
accordance with an eighth embodiment of the present invention.
[0033] FIG. 19 is a flow diagram illustrating a process in
accordance with a eighth embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0034] Hereinafter, preferred embodiments of the present invention
will now be described with reference to the accompanying
drawings.
[0035] A substrate processing apparatus in accordance with an
embodiment is one example of a semiconductor manufacturing
apparatus used to manufacture semiconductor devices (integrated
circuits (ICs)).
[0036] In the following description, a case where a vertical
apparatus for performing a film-forming process on a substrate is
exemplified as the substrate processing apparatus will be
described. However, the present invention is not limited to the
vertical apparatus, but a single-type apparatus may be, for
example, used herein.
[0037] <Overall Configuration of Apparatus>
[0038] As shown in FIG. 1, a cassette 100 for accommodating a wafer
200, which is an example of a substrate is used in a substrate
processing apparatus 1. The wafer 200 is made of a material such as
silicon. The substrate processing apparatus 1 includes a case 101,
and a cassette stage 105 is installed inside the case 101. The
cassette 100 is loaded onto the cassette stage 105 or unloaded from
the cassette stage 105 using an in-process transfer device (not
shown).
[0039] The cassette stage 105 is placed by the in-process transfer
device such that a wafer entrance of the cassette 100 can be
directed upward while the wafer 200 in the cassette 100 is held in
a vertical posture. The cassette stage 105 is configured such that
the cassette 100 is rotated 90.degree. counterclockwise in a
longitudinal direction of a back side of the case 101 to place the
wafer 200 in the cassette 100 in a horizontal posture, and to
direct the wafer entrance of the cassette 100 to the back side of
the case 101.
[0040] A cassette shelf 109 is installed about a middle portion of
the case 101 with respect to the backside and a front side thereof,
and the cassette shelf 109 is configured to store a plurality of
cassettes 100 in a plurality of columns and a plurality of
rows.
[0041] A transfer shelf 123 into which the cassette 100 is to be
transferred by a wafer transfer mechanism 125 is installed in the
cassette shelf 109.
[0042] A spare cassette shelf 110 is installed above the cassette
stage 105, and stores the cassette 100 in reserve.
[0043] A cassette transfer device 115 is installed between the
cassette stage 105 and the cassette shelf 109. The cassette
transfer device 115 is composed of a cassette elevator 115a capable
of moving up and down while holding the cassette 100, and a
cassette transfer mechanism 115b serving as a transfer mechanism.
The cassette transfer device 115 is configured to transfer the
cassette 100 among the cassette stage 105, the cassette shelf 109,
and the spare cassette shelf 110 by a continuous operation of the
cassette elevator 115a and the cassette transfer mechanism
115b.
[0044] A wafer transfer mechanism 125 is installed in the rear of
the cassette shelf 109. The wafer transfer mechanism 125 is
composed of a wafer transfer device 125a capable of rotating or
linearly moving the wafer 200 in a horizontal direction, and a
wafer transfer device elevator 125b for elevating the wafer
transfer device 125a. Tweezers 125c for picking up the wafer 200
are installed in the wafer transfer device 125a. The wafer transfer
mechanism 125 is configured to load (charge) the wafer 200 into a
boat 217 or unload (discharge) the wafer 200 from the boat 217 by a
continuous operation of the wafer transfer device 125a and the
wafer transfer device elevator 125b using the tweezers 125c as a
placing unit of the wafer 200.
[0045] A processing furnace 202 for thermally processing the wafer
200 is installed above the rear of the case 101, and a lower end of
the processing furnace 202 is configured to be opened and closed by
means of a furnace port shutter 116.
[0046] A boat elevator 121 for elevating the boat 217 with respect
to the processing furnace 202 is installed below the processing
furnace 202. An arm 122 is connected to an elevation stage of the
boat elevator 121, and a seal cap 219 is horizontally installed in
the arm 122. The seal cap 219 is configured to be able to
vertically support the boat 217 and close the lower end of the
processing furnace 202.
[0047] The boat 217 includes a plurality of holding members, and is
configured to horizontally hold a plurality of (for example,
approximately 50 to 150) wafers 200 in a state where the plurality
of wafers 200 are arranged in a vertical direction from the center
of the boat 217.
[0048] A cleaning unit 134a for supplying clean air having a
cleaned atmosphere is installed above the cassette shelf 109. The
cleaning unit 134a is composed of a supply fan and a dust-proof
filter, and is configured to allow the clean air to flow inside the
case 101.
[0049] A cleaning unit 134b for supplying clean air is installed in
a left side end of the case 101. In addition, the cleaning unit
134b is composed of a supply fan and a dust-proof filter, and is
configured to allow the clean air to flow around the wafer transfer
device 125a and the boat 217. The clean air is intended to be
exhausted out of the case 101 after it flows around the wafer
transfer device 125a and the boat 217.
[0050] <Operation of Processing Apparatus>
[0051] Next, a main operation of the substrate processing apparatus
1 will be described.
[0052] When the cassette 100 is loaded onto the cassette stage 105
by means of the in-process transfer device (not shown), the
cassette 100 is placed to hold the wafer 200 on the cassette stage
105 in a vertical posture, and direct the wafer entrance of the
cassette 100 upward. Thereafter, the cassette 100 is rotated
90.degree. counterclockwise in a longitudinal direction to the
backward of the case 101 so that the wafer 200 in the cassette 100
can be in a horizontal posture, and the wafer entrance of the
cassette 100 can be directed to the backward of the case 101 by the
cassette stage 105.
[0053] Then, the cassette 100 is automatically transferred and
placed to a preset shelf position of the cassette shelf 109 or the
spare cassette shelf 110 by means of the cassette transfer device
115, temporarily stored, and transferred from the cassette shelf
100 or the spare cassette shelf 110 into the transfer shelf 123 by
means of the cassette transfer device 115, or directly transferred
into the transfer shelf 123.
[0054] When the cassette 100 is transferred to the transfer shelf
123, the wafer 200 is picked up from the cassette 100 via the wafer
entrance by means of the tweezers 125c of the wafer transfer device
125a, and loaded (charged) into the boat 217. The wafer transfer
device 125a placing the wafer 200 into the boat 217 returns to the
cassette 100, and charges another wafer 200 into the boat 217.
[0055] When a preset number of wafers 200 are charged into the boat
217, the furnace port shutter 116 covering the lower end of the
processing furnace 202 is opened, and the lower end of the
processing furnace 202 is then opened. Thereafter, the boat 217
holding a group of the wafers 200 is loaded into the processing
furnace 202 by an elevation operation of the boat elevator 121, and
a lower portion of the processing furnace 202 is closed by the seal
cap 219.
[0056] After the loading process, the wafers 200 are optionally
processed in the processing furnace 202. After the optional
processing, the wafers 200 and the cassette 100 are unloaded from
the case 101 in reverse order as described above.
[0057] <Configuration of Processing Furnace>
[0058] Next, the processing furnace 202 applied to the
above-described substrate processing apparatus will be described
with reference to FIGS. 2 and 3.
[0059] As shown in FIGS. 2 and 3, a heater 207 that is a heating
device (heating means) for heating the wafer 200 is installed in
the processing furnace 202. The heater 207 includes a cylindrical
heat insulating member having a closed top portion, and a plurality
of heater wires, and has a unit configuration in which the heater
wires are installed with respect to the heat insulating member. A
reaction tube 203 made of quartz for processing the wafer 200 is
installed inside the heater 207.
[0060] A manifold 209 made of stainless steel is installed in a
lower end of the reaction tube 203 via an O-ring 220 serving as a
sealing member. An opening in a lower end of the manifold 209 is
air-tightly closed via the O-ring 220 by the seal cap 219 serving
as a lid (cover). A processing chamber 201 is formed in the
processing furnace 202 by at least the reaction tube 203, the
manifold 209 and the seal cap 219.
[0061] A boat support 218 for supporting the boat 217 is installed
in the seal cap 219. As shown in FIG. 1, the boat 217 includes a
bottom plate 210 fixed to the boat support 218 and a top plate 211
arranged above the bottom plate 210, and has a configuration in
which a plurality of posts 221 are installed between the bottom
plate 210 and the top plate 211. A plurality of wafers 200 are held
by the boat 217. The plurality of wafers 200 are supported by the
post 221 of the boat 217 in a state where the wafers 200 are
arranged at regular intervals and held in a horizontal posture.
[0062] In the above-described processing furnace 202, the boat 217
is inserted into the processing chamber 201 while being supported
by the boat support 218 in a state where the plurality of wafers
200 to be batch-processed are stacked in multiple stages on the
boat 217, and the heater 207 is configured to heat the wafer 200
inserted into the processing chamber 201 at a predetermined
temperature.
[0063] As shown in FIGS. 2 and 3, a gas supply tube 310 (a first
gas supply tube) for supplying a first processing gas serving as a
source gas and a gas supply tube 320 (a second gas supply tube) for
supplying a second processing gas serving as a modification gas are
connected to the processing chamber 201.
[0064] A mass flow controller 312 serving as a mass flow control
device (mass flow control means), an evaporator 700 serving as an
evaporation unit (evaporation means) and a valve 314 serving as a
switching valve are installed in the gas supply tube 310 in order
from an upstream side thereof. A nozzle 410 (a first nozzle) is
connected to a front end of the gas supply tube 310. The first
nozzle 410 extends from an arc-shaped space, which is formed
between the wafer 200 and an inner wall of the reaction tube 203
constituting the processing chamber 201, in up and down directions
(a stacking direction of the wafers 200) along the inner wall of
the reaction tube 203. A plurality of gas supply holes 410a for
supplying the first processing gas are installed in a side surface
of the first nozzle 410. The gas supply holes 410a have opening
areas that are inclined or equal in size from the bottom to the top
thereof, and are installed at the same opening pitch.
[0065] In addition, a vent line 610 and a valve 614 connected to an
exhaust pipe 231 to be described later are installed between the
evaporator 700 and the valve 314 in the gas supply tube 310.
Therefore, when the first processing gas is not supplied into the
processing chamber 201, the first processing gas is supplied into
the vent line 610 via the valve 614.
[0066] In addition, a carrier gas supply tube 510 for supplying a
carrier gas is connected to the gas supply tube 310. A mass flow
controller 512 and a valve 514 are installed in the carrier gas
supply tube 510.
[0067] A mass flow controller 322 serving as a mass flow control
device (mass flow control means) and a valve 324 are installed in
the gas supply tube 320 in order from an upstream side thereof. A
nozzle 420 (a second nozzle) is connected to a front end of the gas
supply tube 320. Similar to the first nozzle 410, the second nozzle
420 also extends from an arc-shaped space, which is formed between
the wafer 200 and an inner wall of the reaction tube 203
constituting the processing chamber 201, in up and down directions
(a stacking direction of the wafers 200) along the inner wall of
the reaction tube 203. A plurality of gas supply holes 420a for
supplying the second processing gas are installed in a side surface
of the second nozzle 420. Similar to the gas supply holes 410a, the
gas supply holes 420a have opening areas that are inclined or equal
in size from the bottom to the top thereof, and are installed at
the same opening pitch.
[0068] In addition, a carrier gas supply tube 520 for supplying a
carrier gas is connected to the gas supply tube 320. A mass flow
controller 522 and a valve 524 are installed in the carrier gas
supply tube 520.
[0069] For example, when a first processing gas source supplied
from the gas supply tube 310 is in a liquid state, a first
processing gas serving as a reactive gas is supplied via the first
nozzle 410 into the processing chamber 201 from the gas supply tube
310 which is linked with the carrier gas supply tube 510 via the
mass flow controller 312, the evaporator 700, and the valve 314.
For example, when a source supplied from the gas supply tube 310 is
in a gaseous state, the mass flow controller 312 is exchanged with
a gas mass flow controller, and the use of the evaporator 700 is
not necessary. In addition, a second processing gas serving as a
modification gas is supplied via the second nozzle 420 into the
processing chamber 201 from the gas supply tube 310 which is linked
with the carrier gas supply tube 520 via the mass flow controller
322 and the valve 324.
[0070] As one example of the configuration, a Ti source such as
titanium tetrachloride (TiCl.sub.4), tetrakisdimethylaminotitanium
(TDMAT, Ti[N(CH.sub.3).sub.2].sub.4) or
tetrakisdiethylaminotitanium (TDEAT,
Ti[N(CH.sub.2CH.sub.3).sub.2].sub.4) is introduced as one example
of the first processing gas into the gas supply tube 310. A nitride
source such as ammonia (NH.sub.3), nitrogen (N.sub.2), nitrous
oxide (N.sub.2O) or monomethylhydrazine (CH.sub.6N.sub.2) is
introduced as one example of the second processing gas into the gas
supply tube 320.
[0071] An exhaust pipe 231 for exhausting an inside of the
processing chamber 201 via a valve 243 is connected to the
processing chamber 201. A vacuum pump 246 serving as an exhaust
device (exhaust means) is connected to the exhaust pipe 231, and is
configured to be able to vacuum-exhaust the inside of the
processing chamber 201 by action of the vacuum pump 246. The valve
243 is a switching valve that can start and stop the vacuum exhaust
of the processing chamber 201 by means of a switching operation,
and control an opening level of the valve to adjust an inner
pressure of the processing chamber 201 as well.
[0072] A boat 217 is installed in a central region in the reaction
tube 203. The boat 217 is configured to be able to move up and down
(go in and out) with respect to the reaction tube 203 by means of
the boat elevator 121. A boat rotation mechanism 267 for rotating
the boat 217 to improve processing uniformity is installed in a
lower end of the boat support 218 configured to support the boat
217. The boat 217 supported by the boat support 218 may be rotated
by driving the boat rotation mechanism 267.
[0073] Each of the above-described members such as the mass flow
controllers 312, 322, 512 and 522, the valves 314, 324, 514, 524,
243 and 614, the heater 207, the vacuum pump 246, the boat rotation
mechanism 267 and the boat elevator 121 is connected to a
controller 280. The controller 280 is one example of a control unit
(control means) for controlling the whole operation of the
substrate processing apparatus 1, and is configured to control
adjustment of a flow rate of the mass flow controllers 312, 322,
512 and 522, a switching operation of the valves 314, 324, 514, 524
and 614, switching and pressure-adjustment operations of the valve
243, adjustment of a temperature of the heater 207, start and stop
of the vacuum pump 246, adjustment of a rotary speed of the boat
rotation mechanism 267, an elevating operation of the boat elevator
121, etc.
[0074] <Method of Manufacturing Semiconductor Device>
[0075] Next, as one of processes of manufacturing a semiconductor
device, a method of forming an insulation film on a substrate using
the processing furnace 202 of the above-described substrate
processing apparatus during a manufacturing of a large scale
integration (LSI) IC will be described.
[0076] In addition, in the following description, an operation of
each of the parts constituting the substrate processing apparatus
is controlled by the controller 280.
[0077] As a method of forming a TiN film as a conductive film on a
substrate, an example wherein the TiCl.sub.4 is used as a
titanium-containing source which is a first processing gas and the
NH.sub.3 is used as a nitriding gas which is a second processing
gas will be described.
[0078] First, an example wherein a film is formed by a CVD method
through a process in which one cycle of the film-forming sequence
is composed of one pulse of the Ti source and two or more pulses of
the N source will be described.
First Embodiment
[0079] FIG. 4 illustrates a film-forming sequence of a TiN film
according to a first embodiment. In addition, FIG. 5 is a flow
diagram illustrating a process in accordance with the first
embodiment.
[0080] In the film-forming process, the controller 280 controls the
substrate processing apparatus 1 in a following manner. That is,
the heater 207 maintains a temperature of the processing chamber
201 at which a CVD reaction occurs, for example, within a range of
250.degree. C. to 800.degree. C., preferably 700.degree. C. or
less, and more preferably 450.degree. C. Thereafter, the plurality
of wafers 200 are charged into the boat 217, and the boat 217 is
loaded into the processing chamber 201. Subsequently, the boat 217
is rotated by the boat drive mechanism 267 to rotate the wafers
200. Thereafter, the valve 243 is opened and the vacuum pump 246 is
operated to evacuate the inside of the processing chamber 201. When
a temperature of the wafers 200 reaches 450.degree. C. and the
temperature is stabilized, a sequence to be described later is
performed with the temperature of the processing chamber 201 being
maintained at 450.degree. C.
[0081] For a deposition of a TiN film by the CVD method, the
controller 280 controls valves, mass flow controllers and a vacuum
pump to supply the TiCl.sub.4 and the NH.sub.3 into the processing
chamber 201 such that both the TiCl.sub.4 and the NH.sub.3 are
present in the processing chamber 201 during a certain time period
to cause a gas phase reaction (CVD reaction). Hereinafter, the
film-forming sequence will now be described in detail.
[0082] The TiCl.sub.4 is in a liquid state at room temperature.
While the TiCl.sub.4 may be gasified by heating and supplied into
the processing chamber 201 or the TiCl.sub.4 may be supplied into
the processing chamber 201 by passing an inert gas (referred to as
a carrier gas) such as helium (He), neon (Ne), argon (Ar) and
nitrogen (N.sub.2) through a the TiCl.sub.4 container using the
evaporator 700 and supplying the evaporated the TiCl.sub.4 along
with the carrier gas into the processing chamber 201, the latter
will be exemplified.
[0083] In the sequence, a step of simultaneously flowing the
TiCl.sub.4 and the NH.sub.3 is performed.
[0084] Since the CVD reaction occurs between the first processing
gas, for example, the TiCl.sub.4, and the second processing gas,
for example, the NH.sub.3, by supplying the first processing gas
and the second processing gas simultaneously, a higher film-forming
rate may be achieved compared to an ALD reaction. More
particularly, the TiCl.sub.4 is introduced into the gas supply tube
310, and the carrier gas (N.sub.2) is introduced into the carrier
gas supply tube 510. The valve 314 of the gas supply tube 310, the
valve 514 of the carrier gas supply tube 510, and the valve 243 of
the exhaust pipe 231 are opened. The carrier gas flows from the
carrier gas supply tube 510, and a flow rate thereof is then
adjusted by the mass flow controller 512. The TiCl.sub.4 flows from
the gas supply tube 310, and a flow rate thereof is then adjusted
by the mass flow controller 312. The TiCl.sub.4 is evaporated by
the evaporator 700, mixed with the flow rate-controlled carrier
gas, and supplied from the gas supply hole 410a of the first nozzle
410 into the processing chamber 201.
[0085] In addition, the NH.sub.3 is introduced into the gas supply
tube 320, and a carrier gas (N.sub.2) is introduced into the
carrier gas supply tube 520. The valve 324 of the gas supply tube
320, the valve 524 of the carrier gas supply tube 520 and the valve
243 of the exhaust pipe 231 are opened. The carrier gas flows from
the carrier gas supply tube 520, and a flow rate thereof is then
adjusted by the mass flow controller 522. The NH.sub.3 flows from
the gas supply tube 320, and a flow rate thereof is then adjusted
by the mass flow controller 322, mixed with the flow
rate-controlled carrier gas, and supplied from the gas supply hole
420a of the second nozzle 420 into the processing chamber 201.
[0086] In addition, the TiCl.sub.4 and the NH.sub.3 supplied into
the processing chamber 201 are exhausted through the exhaust pipe
231. In this case, an opening level of the valve 243 is suitably
adjusted to maintain the inner pressure of the processing chamber
201 within a range of 5 to 50 Pa, for example, 20 Pa. A supply
quantity of the TiCl.sub.4 controlled by the mass flow controller
312 ranges from 0.8 to 3.0 g/min. A supply quantity of the NH.sub.3
controlled by the mass flow controller 322 ranges from 0.3 to 15
slm. The wafer 200 is exposed to the TiCl.sub.4 and the NH.sub.3
until a film reaches a desired thickness. In this case, a
temperature of the heater 207 is set such that a temperature of the
wafer 200 ranges from 250.degree. C. to 800.degree. C., for
example, 450.degree. C. In addition, when the temperature of the
wafer 200 is, for example, less than 250.degree. C., a reaction
speed of the TiCl.sub.4 and the NH.sub.3 is slow. Therefore,
obtaining the film having the desired thickness within a
predetermined time period is difficult, and the practical
industrial use of the film is also impossible. Accordingly, the
temperature of the wafer 200 preferably ranges from 300.degree. C.
to 500.degree. C. to sufficiently induce the CVD reaction at a high
speed.
[0087] (Step S11)
[0088] In step S11, in order to form the TiN film on a substrate
using a high-speed CVD method, the TiCl.sub.4 is supplied through
the first nozzle 410, and the NH.sub.3 is supplied together with
the TiCl.sub.4 through the second nozzle 420. The TiCl.sub.4 is
introduced into the gas supply tube 310, the NH.sub.3 is introduced
into the gas supply tube 320, and the carrier gas (N.sub.2) is
introduced into the carrier gas supply tubes 510 and 520. The
valves 314 and 324 of the gas supply tube 310 and 320, the valves
514 and 524 of the carrier gas supply tubes 510 and 520, and the
valve 243 of the exhaust pipe 231 are opened together. The carrier
gas flows from the carrier gas supply tubes 510 and 520, and a flow
rate thereof is then adjusted by the mass flow controllers 512 and
522. The TiCl.sub.4 flows from the gas supply tube 310, and the
flow rate thereof is then adjusted by the mass flow controller 312.
The TiCl.sub.4 is evaporated by the evaporator 700, mixed with the
flow rate-controlled carrier gas, and exhausted from the exhaust
pipe 231 while being supplied from the gas supply hole 410a of the
first nozzle 410 into the processing chamber 201. The NH.sub.3
flows from the gas supply tube 320, and the flow rate thereof is
then adjusted by the mass flow controller 322. The NH.sub.3 is
mixed with the flow rate-controlled carrier gas, and exhausted from
the exhaust pipe 231 while being supplied from the gas supply hole
420a of the second nozzle 420 into the processing chamber 201.
[0089] In this case, the opening level of the valve 243 is suitably
adjusted to maintain the inner pressure of the processing chamber
201 within a range of 20 to 50 Pa, for example, 30 Pa. A supply
quantity of the TiCl.sub.4 controlled by the mass flow controller
312 is, for example, ranges from 0.8 to 1.5 g/min. In addition, a
supply flow rate of the NH.sub.3 controlled by the mass flow
controller 322 ranges, for example, from 5.0 to 8.0 slm. A time
period during which the wafer 200 is exposed to the TiCl.sub.4 and
the NH.sub.3 ranges, for example, from 5 to 30 seconds.
[0090] In this case, a gas flowing into the processing chamber 201
is an inert gas such as the TiCl.sub.4, the NH.sub.3 and N.sub.2. A
gas phase reaction (thermal CVD reaction) occurs between the
TiCl.sub.4 and the NH.sub.3 such that a titanium nitride layer
having a predetermined film thickness is deposited on a surface or
an underlying layer of the wafer 200. Here, in addition to the
continuous layer made of titanium nitride, the titanium nitride
layer includes discontinuous layers, thin films obtained by
overlapping the discontinuous layers, or thin films to which other
elements are added. In addition, the continuous layer made of
titanium nitride is often referred to as a titanium nitride thin
film.
[0091] (Step S12)
[0092] In step S12, the valve 314 of the gas supply tube 310 is
closed to stop the supply of the TiCl.sub.4 into the processing
chamber 201, and the valve 614 is opened to flow the TiCl.sub.4
through the vent line 610. As a result, the TiCl.sub.4 may be
stably supplied into the processing chamber. Here, a time period
during which the wafer 200 is exposed to the NH.sub.3 after the
supply of the TiCl.sub.4 is stopped ranges, for example, from 0.1
to 30 seconds.
[0093] (Steps 13)
[0094] In step S13, the valve 324 of the gas supply tube 320 is
closed to stop the supply of the NH.sub.3 into the processing
chamber 201. In this case, the valve 243 of the gas exhaust pipe
231 is opened to exhaust the inside of the processing chamber 201
using the vacuum pump 246 until the inner pressure of the
processing chamber 201 reaches 20 Pa or less to discharge the
remaining the TiCl.sub.4 and the NH.sub.3 from the processing
chamber 201. In this case, when the switching valve 514 and the
switching valve 524 are kept open to supply an inert gas such as
N.sub.2 into the processing chamber 201 from the carrier gas supply
tube 510 connected on the way to the gas supply tube 310 and the
carrier gas supply tube 520 connected on the way to the gas supply
tube 320, the remaining the TiCl.sub.4 and the NH.sub.3 may be
discharged more effectively. In addition, a gas such as the
TiCl.sub.4 and the NH.sub.3 can be prevented from entering the gas
supply tube 310 and the gas supply tube 320 from the processing
chamber 201. Here, a time taken to remove an inner atmosphere of
the processing chamber ranges, for example, from 3 to 10
seconds.
[0095] That is, after the source gas, the TiCl.sub.4, and the
modification gas, the NH.sub.3, are supplied simultaneously, a
film-forming cycle is completed with a modification process by
first stopping the supply of the source gas and then stopping the
supply of the modification gas (delaying a time point required to
stop the supply of the modification gas). Therefore, reducing a
ratio of Cl remaining in the film is possible. In addition, after
the source gas and the modification gas are supplied separately or
simultaneously, both or either of the source gas and the
modification gas to be supplied next may effectively react with
each other by stopping the supply of a gas to remove products (the
source gas, the modification gas, and intermediates, and byproducts
thereof) remaining in the reaction chamber.
[0096] (Step S14)
[0097] In step S14, the valve 324 of the gas supply tube 320 is
opened to supply the NH.sub.3 into the processing chamber.
[0098] In this case, an opening level of the valve 243 is suitably
adjusted to maintain the inner pressure of the processing chamber
201 within a range of 20 to 50 Pa, for example, 30 Pa. A supply
flow rate of the NH.sub.3 controlled by the mass flow controller
322 ranges, for example, from 5.0 to 8.0 slm. A time taken to
expose the wafer 200 to the NH.sub.3 ranges, for example, from 5 to
30 seconds.
[0099] That is, after the source gas and the modification gas are
supplied simultaneously, an ALD reaction between the modification
gas and the source gas deposited onto the substrate may be caused
to facilitate generation of byproducts (HCl, etc.) by stopping the
supply of both the source gas and the modification gas, removing
products (the source gas, the modification gas, and intermediates
and byproducts thereof) remaining in the reaction chamber and
exposing the substrate to only the modification gas, the NH.sub.3.
Therefore, effective removal of Cl in the film is possible.
[0100] (Step S15)
[0101] The valve 324 of the gas supply tube 320 is closed to stop
the supply of the NH.sub.3 into the processing chamber 201. In this
case, the valve 243 of the gas exhaust pipe 231 is kept open to
exhaust the inside of the processing chamber 201 using the vacuum
pump 246 until the inner pressure of the processing chamber 201
reaches 20 Pa or less, and discharge the remaining the NH.sub.3
from the processing chamber 201. In this case, when an inert gas
such as N.sub.2 is supplied into the processing chamber 201, the
remaining the NH.sub.3 may be discharged more effectively. A time
taken to discharge NH.sub.3 in the processing chamber 201 ranges,
for example, from 3 to 10 seconds.
[0102] A TiN film having a predetermined film thickness is formed
on the wafer 200 using many kinds of other CVD methods while
removing a gas in the processing chamber 201 by performing steps
S11 through S15 as one cycle once or a predetermined number of
times. In addition, the reaction may be facilitated by applying
plasma or irradiating light during the above-described
sequence.
[0103] Hereinafter, only parts of this embodiment different from
those of the first embodiment will now be described.
Second Embodiment
[0104] FIG. 6 shows a sequence according to a second embodiment. In
addition, FIG. 7 is a flow diagram illustrating a process according
to the second embodiment. The sequence according to the second
embodiment will be described with reference to FIGS. 6 and 7.
[0105] (Step S21)
[0106] In step S21, the valve 324 of the gas supply tube 320 is
opened to supply the NH.sub.3 into the processing chamber 201. A
time taken to expose the wafer 200 to the NH.sub.3 ranges, for
example, from 0.1 to 30 seconds.
[0107] (Step S22)
[0108] Next, the valve 314 of the gas supply tube 310 is opened to
supply the TiCl.sub.4 into the processing chamber 201. A time taken
to expose the wafer 200 to the TiCl.sub.4 and the NH.sub.3 ranges,
for example, from 5 to 30 seconds.
[0109] (Step S23)
[0110] In step S23, the valve 314 of the gas supply tube 310 is
closed to stop the supply of the TiCl.sub.4 into the processing
chamber 201, and the valve 614 is open to allow the TiCl.sub.4 to
flow into the vent line 610. The supply of the TiCl.sub.4 into the
processing chamber 201 is stopped, and A time period during which
the wafer 200 is exposed to the NH.sub.3 ranges, for example, from
0.1 to 30 seconds.
[0111] (Step S24)
[0112] In step S24, the valve 324 of the gas supply tube 320 is
closed to stop the supply of the NH.sub.3 into the processing
chamber 201. In this case, the valve 243 of the gas exhaust pipe
231 is kept open to exhaust the inside of the processing chamber
201 using the vacuum pump 246 until the inner pressure of the
processing chamber 201 reaches 20 Pa or less, and discharge the
remaining the TiCl.sub.4 and the NH.sub.3 from the processing
chamber 201. In this case, when an inert gas such as N.sub.2 is
supplied into the processing chamber 201, the remaining the
TiCl.sub.4 and the NH.sub.3 may be discharged more effectively. A
time taken to remove an inner atmosphere of the processing chamber
ranges, for example, from 3 to 10 seconds.
[0113] (Step S25)
[0114] In step S25, the valve 324 of the gas supply tube 320 is
opened to supply the NH.sub.3 into the processing chamber 201. A
time taken to expose the wafer 200 to the NH.sub.3 ranges, for
example, from 5 to 30 seconds.
[0115] (Step S26)
[0116] The valve 324 of the gas supply tube 320 is closed to stop
the supply of the NH.sub.3 into the processing chamber 201, In this
case, the valve 243 of the gas exhaust pipe 231 is kept open to
exhaust the inside of the processing chamber 201 using the vacuum
pump 246 until the inner pressure of the processing chamber 201
reaches 20 Pa or less, and discharge the remaining the NH.sub.3
from the processing chamber 201. In this case, when an inert gas
such as N.sub.2 is supplied into the processing chamber 201, the
remaining the NH.sub.3 may be discharged more effectively. A time
taken to discharge NH.sub.3 in the processing chamber 201 ranges,
for example, from 3 to 10 seconds.
[0117] A TiN film having a predetermined film thickness is formed
on the wafer 200 using many kinds of other CVD methods while
removing a gas in the processing chamber 201 by performing steps
S21 through S26 as one cycle once or a predetermined number of
times.
[0118] According to the second embodiment, since a CVD reaction
between the source gas and the modification gas is caused by
supplying the source gas and the modification gas simultaneously, a
higher film-forming rate may be achieved compared to the ALD
reaction. After the source gas and the modification gas are
supplied simultaneously, a film-forming cycle is completed with a
modification process by first stopping the supply of the source gas
and then stopping the supply of the modification gas (delaying a
time point required to stop the supply of the modification gas).
Therefore, reducing a ratio of Cl remaining in the film is
possible. In addition, after the source gas and the modification
gas are supplied separately or simultaneously, both or either of
the source gas and the modification gas to be supplied next may
effectively react with each other by stopping the supply of a gas
to remove products (the source gas, the modification gas, and
intermediates and byproducts thereof) remaining in the reaction
chamber. In addition, after the source gas and the modification gas
are supplied simultaneously, an ALD reaction between the
modification gas and the source gas deposited onto the substrate
may be caused to facilitate generation of byproducts (HCl, etc.) by
stopping the supply of both the source gas and the modification
gas, removing products (the source gas, the modification gas, and
intermediates and byproducts thereof) remaining in the reaction
chamber, and exposing the substrate to only the modification gas,
the NH.sub.3. Therefore, effective removal of Cl in the film is
possible. Even when the source gas and the modification gas are
also supplied simultaneously, time points for the supply of the
source gas and the modification gas are slightly different at every
cycle. Therefore, the film thickness may be varied at every cycle.
From these facts, a supply time of the source gas may be maintained
nearly at a constant level between batches by supplying the source
gas, the TiCl.sub.4, after the modification gas, the NH.sub.3, is
supplied as described in this embodiment, and stopping the supply
of the source gas in a state where the modification gas is being
supplied. Therefore, a film thickness of the film formed in the CVD
reaction can be controlled using only a pulse of the source
gas.
Third Embodiment
[0119] FIG. 8 shows a sequence according to a third embodiment. In
addition, FIG. 9 is a flow diagram illustrating a process according
to the third embodiment. Hereinafter the sequence according to the
third embodiment will now be described with reference to FIGS. 8
and 9.
[0120] (Step S31)
[0121] In step S31, the valve 314 of the gas supply tube 310 is
opened to supply the TiCl.sub.4 into the processing chamber 201. A
time taken to expose the wafer 200 to the TiCl.sub.4 ranges, for
example, from 0.1 to 30 seconds.
[0122] (Step S32)
[0123] Next, the valve 324 of the gas supply tube 320 is opened to
supply the NH.sub.3 into the processing chamber 201. Here, A time
period during which the wafer 200 is exposed to the TiCl.sub.4 and
the NH.sub.3 ranges, for example, from 5 to 30 seconds.
[0124] (Step S33)
[0125] In step S33, the valve 314 of the gas supply tube 310 is
closed to stop the supply of the TiCl.sub.4 into the processing
chamber 201, and the valve 614 is open to allow the TiCl.sub.4 to
flow into the vent line 610. The supply of the TiCl.sub.4 is
stopped, and A time period during which the wafer 200 is exposed to
the NH.sub.3 ranges, for example, from 0.1 to 30 seconds.
[0126] (Step S34)
[0127] In step S34, the valve 324 of the gas supply tube 320 is
closed to stop the supply of the NH.sub.3 into the processing
chamber 201. In this case, the valve 243 of the gas exhaust pipe
231 is kept open to exhaust the inside of the processing chamber
201 using the vacuum pump 246 until the inner pressure of the
processing chamber 201 reaches 20 Pa or less, and discharge the
remaining the TiCl.sub.4 and the NH.sub.3 from the processing
chamber 201. In this case, when an inert gas such as N.sub.2 is
supplied into the processing chamber 201, the remaining the
TiCl.sub.4 and the NH.sub.3 may be discharged more effectively. A
time taken to remove an inner atmosphere of the processing chamber
201 ranges, for example, from 3 to 10 seconds.
[0128] (Step S35)
[0129] In step S35, the valve 324 of the gas supply tube 320 is
opened to supply the NH.sub.3 into the processing chamber 201. A
time taken to expose the wafer 200 to the NH.sub.3 ranges, for
example, from 5 to 30 seconds.
[0130] (Step S36)
[0131] The valve 324 of the gas supply tube 320 is closed to stop
the supply of the NH.sub.3 into the processing chamber 201. In this
case, the valve 243 of the gas exhaust pipe 231 is kept open to
exhaust the inside of the processing chamber 201 using the vacuum
pump 246 until the inner pressure of the processing chamber 201
reaches 20 Pa or less, and discharge the remaining the NH.sub.3
from the processing chamber 201. In this case, when an inert gas
such as N.sub.2 is supplied into the processing chamber 201, the
remaining the NH.sub.3 may be discharged more effectively. A time
taken to discharge NH.sub.3 in the processing chamber 201 ranges,
for example, from 3 to 10 seconds.
[0132] A TiN film having a predetermined film thickness is formed
on the wafer 200 using many kinds of other CVD methods while
removing a gas in the processing chamber 201 by performing steps
S31 through S36 as one cycle once or a predetermined number of
times.
[0133] According to the third embodiment, since a CVD reaction
between the source gas and the modification gas is caused by
supplying the source gas and the modification gas simultaneously, a
higher film-forming rate may be achieved compared to the ALD
reaction. After the source gas and the modification gas are
supplied simultaneously, a film-forming cycle is completed with a
modification process by first stopping the supply of the source gas
and then stopping the supply of the modification gas (delaying a
time point required to stop the supply of the modification gas).
Therefore, reducing a ratio of Cl remaining in the film is
possible. In addition, after the source gas and the modification
gas are supplied separately or simultaneously, both or either of
the source gas and the modification gas to be supplied next may
effectively react with each other by stopping the supply of a gas
to remove products (the source gas, the modification gas, and
intermediates and byproducts thereof) remaining in the reaction
chamber. In addition, after the source gas and the modification gas
are supplied simultaneously, an ALD reaction between the
modification gas and the source gas deposited onto the substrate
may be caused to facilitate generation of byproducts (HCl, etc.) by
stopping the supply of both the source gas and the modification
gas, removing products (the source gas, the modification gas, and
intermediates and byproducts thereof) remaining in the reaction
chamber, and exposing the substrate to only the modification gas,
the NH.sub.3. Therefore, effective removal of Cl in the film is
possible. Before the CVD reaction between the source gas, the
TiCl.sub.4, and the modification gas, the NH.sub.3, seed crystals
having a low Cl concentration may also be formed on the substrate
by exposing the substrate to only the source gas, the TiCl.sub.4,
to adsorb the source gas and intermediates thereof onto the
substrate during the ALD reaction.
Fourth Embodiment
[0134] FIG. 10 shows a sequence according to a fourth embodiment.
In addition, FIG. 11 is a flow diagram illustrating a process
according to the fourth embodiment. Hereinafter the sequence
according to the fourth embodiment will now be described with
reference to FIGS. 10 and 11.
[0135] (Step S41)
[0136] In step S41, the valve 314 of the gas supply tube 310 is
opened to supply the TiCl.sub.4 into the processing chamber 201. A
time taken to expose the wafer 200 to the TiCl.sub.4 ranges, for
example, from 0.1 to 30 seconds.
[0137] (Step S42)
[0138] Next, the valve 324 of the gas supply tube 320 is opened to
supply the NH.sub.3 into the processing chamber 201. Here, A time
period during which the wafer 200 is exposed to the TiCl.sub.4 and
the NH.sub.3 ranges, for example, from 5 to 30 seconds.
[0139] (Step S43)
[0140] In step S43, the valve 324 of the gas supply tube 320 is
closed to stop the supply of the NH.sub.3 into the processing
chamber 201. The supply of the NH.sub.3 is stopped, and A time
period during which the wafer 200 is exposed to the TiCl.sub.4
ranges, for example, from 0.1 to 30 seconds.
[0141] (Step S44)
[0142] In step S44, the valve 314 of the gas supply tube 310 is
closed to stop the supply of the TiCl.sub.4 into the processing
chamber 201, and the valve 614 is opened to allow the TiCl.sub.4 to
flow into the vent line 610. In this case, the valve 243 of the gas
exhaust pipe 231 is kept open to exhaust the inside of the
processing chamber 201 using the vacuum pump 246 until the inner
pressure of the processing chamber 201 reaches 20 Pa or less, and
discharge the remaining the TiCl.sub.4 and the NH.sub.3 from the
processing chamber 201. In this case, when an inert gas such as
N.sub.2 is supplied into the processing chamber 201, the remaining
the TiCl.sub.4 and the NH.sub.3 may be discharged more effectively.
A time taken to remove an inner atmosphere of the processing
chamber 201 ranges, for example, from 3 to 10 seconds.
[0143] (Step S45)
[0144] In step S45, the valve 324 of the gas supply tube 320 is
opened to supply the NH.sub.3 into the processing chamber 201. A
time taken to expose the wafer 200 to the NH.sub.3 ranges, for
example, from 5 to 30 seconds.
[0145] (Step S46)
[0146] The valve 324 of the gas supply tube 320 is closed to stop
the supply of the NH.sub.3 into the processing chamber 201. In this
case, the valve 243 of the gas exhaust pipe 231 is kept open to
exhaust the inside of the processing chamber 201 using the vacuum
pump 246 until the inner pressure of the processing chamber 201
reaches 20 Pa or less, and discharge the remaining the NH.sub.3
from the processing chamber 201. In this case, when an inert gas
such as N.sub.2 is supplied into the processing chamber 201, the
remaining the NH.sub.3 may be discharged more effectively. A time
taken to discharge NH.sub.3 in the processing chamber 201 ranges,
for example, from 3 to 10 seconds.
[0147] A TiN film having a predetermined film thickness is formed
on the wafer 200 using many kinds of other CVD methods while
removing a gas in the processing chamber 201 by performing steps
S41 through S46 as one cycle once or a predetermined number of
times.
[0148] According to the fourth embodiment, since a CVD reaction
between the source gas and the modification gas is caused by
supplying the source gas and the modification gas simultaneously, a
higher film-forming rate may be achieved compared to the ALD
reaction. In addition, after the source gas and the modification
gas are supplied separately or simultaneously, both or either of
the source gas and the modification gas to be supplied next may
effectively react with each other by stopping the supply of a gas
to remove products (the source gas, the modification gas, and
intermediates and byproducts thereof) remaining in the reaction
chamber. In addition, after the source gas and the modification gas
are supplied simultaneously, an ALD reaction between the
modification gas and the source gas deposited onto the substrate
may be caused to facilitate generation of byproducts (HCl, etc.) by
stopping the supply of both the source gas and the modification
gas, removing products (the source gas, the modification gas, and
intermediates and byproducts thereof) remaining in the reaction
chamber, and exposing the substrate to only the modification gas,
the NH.sub.3. Therefore, effective removal of Cl in the film is
possible. Before the CVD reaction between the source gas, the
TiCl.sub.4, and the modification gas, the NH.sub.3, seed crystals
having a low Cl concentration may also be formed on the substrate
by exposing the substrate to only the source gas, the TiCl.sub.4,
to adsorb the source gas and intermediates thereof onto the
substrate during the ALD reaction. Even when the source gas and the
modification gas are also supplied simultaneously, time points for
the supply of the source gas and the modification gas are slightly
different at every cycle. Therefore, the film thickness may be
varied at every cycle. From these facts, unlike the above-described
second embodiment, a supply time of the modification gas may be
maintained nearly at a constant level between batches by supplying
the modification gas, the NH.sub.3, after the source gas, the
TiCl.sub.4, is supplied in this embodiment, and stopping the supply
of the modification gas in a state where the source gas is being
supplied. Therefore, a film thickness of the film formed in the CVD
reaction can be controlled using only a pulse of the modification
gas.
[0149] Next, a case where a film is formed by a CVD method through
a process in which there is a time zone at which pulses of the Ti
source and the N source are in an ON state simultaneously and only
one of the pulses of the Ti source and the N source is in an ON
state in one cycle of the film-forming sequence will be
described.
Fifth Embodiment
[0150] FIG. 12 shows a sequence according to a fifth embodiment. In
addition, FIG. 13 is a flow diagram illustrating a process
according to the fifth embodiment. Hereinafter the sequence
according to the fifth embodiment will now be described with
reference to FIGS. 12 and 13.
[0151] (Step S51)
[0152] In step S51, the valve 314 of the gas supply tube 310 is
opened to start the supply of the TiCl.sub.4. A time taken to
expose the wafer 200 to the TiCl.sub.4 ranges, for example, from
0.1 to 30 seconds.
[0153] (Step S52)
[0154] In step S52, the valve 324 of the gas supply tube 320 is
opened to supply the NH.sub.3 into the processing chamber 201.
Here, A time period during which the wafer 200 is exposed to the
TiCl.sub.4 and the NH.sub.3 ranges, for example, from 5 to 30
seconds.
[0155] (Step S53)
[0156] In step S53, the valve 314 of the gas supply tube 310 is
closed to stop the supply of the TiCl.sub.4 into the processing
chamber 201, and the valve 614 is opened to allow the TiCl.sub.4 to
flow into the vent line 610. The supply of the TiCl.sub.4 is
stopped, and A time period during which the wafer 200 is exposed to
the NH.sub.3 ranges, for example, from 5 to 30 seconds.
[0157] (Step S54)
[0158] In step S54, the valve 324 of the gas supply tube 320 is
closed to stop the supply of the NH.sub.3 into the processing
chamber 201. In this case, the valve 243 of the gas exhaust pipe
231 is kept open to exhaust the inside of the processing chamber
201 using the vacuum pump 246 until the inner pressure of the
processing chamber 201 reaches 20 Pa or less, and discharge the
remaining the TiCl.sub.4 and the NH.sub.3 from the processing
chamber 201. In this case, when an inert gas such as N.sub.2 is
supplied into the processing chamber 201, the remaining the
TiCl.sub.4 and the NH.sub.3 may be discharged more effectively. A
time taken to remove an inner atmosphere of the processing chamber
ranges, for example, from 3 to 10 seconds.
[0159] A TiN film having a predetermined film thickness is formed
on the wafer 200 using many kinds of other CVD methods while
removing a gas in the processing chamber 201 by performing steps
S51 through S54 as one cycle once or a predetermined number of
times.
[0160] According to the fifth embodiment, since a CVD reaction
between the source gas and the modification gas is caused by
supplying the source gas and the modification gas simultaneously, a
higher film-forming rate may be achieved, than the ALD reaction. In
addition, after the source gas and the modification gas are
supplied separately or simultaneously, both or either of the source
gas and the modification gas to be supplied next may effectively
react with each other by stopping the supply of a gas to remove
products (the source gas, the modification gas, and intermediates
and byproducts thereof) remaining in the reaction chamber. Before
the CVD reaction between the source gas, the TiCl.sub.4, and the
modification gas, the NH.sub.3, seed crystals having a low Cl
concentration may also be formed on the substrate by exposing the
substrate to only the source gas, the TiCl.sub.4, to adsorb the
source gas and intermediates thereof onto the substrate during the
ALD reaction.
Sixth Embodiment
[0161] FIG. 14 shows a sequence according to a sixth embodiment. In
addition, FIG. 15 is a flow diagram illustrating a process
according to the sixth embodiment. Hereinafter the sequence
according to the sixth embodiment will now be described with
reference to FIGS. 14 and 15.
[0162] (Step S61)
[0163] In step S61, the valve 324 of the gas supply tube 320 is
opened to supply the NH.sub.3 into the processing chamber 201. A
time taken to expose the wafer 200 to the NH.sub.3 ranges, for
example, from 0.1 to 30 seconds.
[0164] (Step S62)
[0165] In step S62, the valve 314 of the gas supply tube 310 is
opened to start the supply of the TiCl.sub.4. A time taken to
expose the wafer 200 to the TiCl.sub.4 and the NH.sub.3 ranges, for
example, from 5 to 30 seconds.
[0166] (Step S63)
[0167] In step S63, the valve 314 of the gas supply tube 310 is
closed to stop the supply of the TiCl.sub.4 into the processing
chamber 201, and the valve 614 is opened to allow the TiCl.sub.4 to
flow into the vent line 610. The supply of the TiCl.sub.4 is
stopped, and A time period during which the wafer 200 is exposed to
the NH.sub.3 ranges, for example, from 0.1 to 30 seconds.
[0168] (Step S64)
[0169] In step S64, the valve 324 of the gas supply tube 320 is
closed to stop the supply of the NH.sub.3 into the processing
chamber 201. In this case, the valve 243 of the gas exhaust pipe
231 is kept open to exhaust the inside of the processing chamber
201 using the vacuum pump 246 until the inner pressure of the
processing chamber 201 reaches 20 Pa or less, and discharge the
remaining the TiCl.sub.4 and the NH.sub.3 from the processing
chamber 201. In this case, when an inert gas such as N.sub.2 is
supplied into the processing chamber 201, the remaining the
TiCl.sub.4 and the NH.sub.3 may be discharged more effectively. A
time taken to remove an inner atmosphere of the processing chamber
ranges, for example, from 3 to 10 seconds.
[0170] A TiN film having a predetermined film thickness is formed
on the wafer 200 using many kinds of other CVD methods while
removing a gas in the processing chamber 201 by performing steps
S61 through S64 as one cycle once or a predetermined number of
times.
[0171] According to the sixth embodiment, since a CVD reaction
between the source gas and the modification gas is caused by
supplying the source gas and the modification gas simultaneously, a
higher film-forming rate may be achieved compared to the ALD
reaction. In addition, after the source gas and the modification
gas are supplied separately or simultaneously, both or either of
the source gas and the modification gas to be supplied next may
effectively react with each other by stopping the supply of a gas
to remove products (the source gas, the modification gas, and
intermediates and byproducts thereof) remaining in the reaction
chamber. In addition, after the source gas and the modification gas
are supplied simultaneously, an ALD reaction between the
modification gas and the source gas deposited onto the substrate
may be caused to facilitate generation of byproducts (HCl, etc.) by
stopping the supply of both the source gas and the modification
gas, removing products (the source gas, the modification gas, and
intermediates and byproducts thereof) remaining in the reaction
chamber, and exposing the substrate to only the modification gas,
the NH.sub.3. Therefore, effective removal of Cl in the film is
possible. In addition, a supply time of the source gas may be
maintained nearly at a constant level between batches by supplying
the source gas, the TiCl.sub.4, after the modification gas, the
NH.sub.3, is supplied, and stopping the supply of the source gas in
a state where the modification gas is being supplied. Therefore, a
film thickness of the film formed in the CVD reaction can be
controlled using only a pulse of the source gas.
[0172] That is, according to the fifth and sixth embodiments, in
addition to the above-mentioned effects, an equivalent-quality film
may be formed with higher productivity or a high-quality film may
be formed with equivalent productivity compared to when one sheet
of substrate to be processed is processed alone or about two sheets
of substrates, that is, a small number of substrates are processed
simultaneously.
[0173] Next, a case where a film is formed by a CVD method through
a process in which one cycle of the film-forming sequence is
composed of two or more pulses of the Ti source and two or more
pulses of the N source will be described.
Seventh Embodiment
[0174] FIG. 16 shows a sequence according to a seventh embodiment.
In addition, FIG. 17 is a flow diagram illustrating a process
according to the seventh embodiment. Hereinafter the sequence
according to the seventh embodiment will now be described with
reference to FIGS. 16 and 17.
[0175] (Step S71)
[0176] In step S71, the valve 314 of the gas supply tube 310 is
opened to start the supply of the TiCl.sub.4.
[0177] (Step S72)
[0178] In step S72, the valve 314 of the gas supply tube 310 is
closed to stop the supply of the TiCl.sub.4 into the processing
chamber 201, and the valve 614 is opened to allow the TiCl.sub.4 to
flow into the vent line 610. In this case, the valve 243 of the gas
exhaust pipe 231 is kept open to exhaust the inside of the
processing chamber 201 using the vacuum pump 246 until the inner
pressure of the processing chamber 201 reaches 20 Pa or less, and
discharge the remaining the TiCl.sub.4 from the processing chamber
201. In this case, when an inert gas such as N.sub.2 is supplied
into the processing chamber 201, the remaining the TiCl.sub.4 may
be discharged more effectively.
[0179] (Step S73)
[0180] In step S73, the valve 314 of the gas supply tube 310 is
opened to start the supply of the TiCl.sub.4, and the valve 324 of
the gas supply tube 320 is simultaneously opened to supply the
NH.sub.3 into the processing chamber 201.
[0181] (Step S74)
[0182] In step S74, the valve 314 of the gas supply tube 310 is
closed to stop the supply of the TiCl.sub.4 into the processing
chamber, and the valve 614 is opened to allow the TiCl.sub.4 to
flow into the vent line 610 and the valve 324 of the gas supply
tube 320 is simultaneously closed to stop the supply of the
NH.sub.3 into the processing chamber 201. In this case, the valve
243 of the gas exhaust pipe 231 is kept open to exhaust the inside
of the processing chamber 201 using the vacuum pump 246 until the
inner pressure of the processing chamber 201 reaches 20 Pa or less,
and discharge the remaining the TiCl.sub.4 and the NH.sub.3 from
the processing chamber 201. In this case, when an inert gas such as
N.sub.2 is supplied into the processing chamber 201, the remaining
the TiCl.sub.4 and the NH.sub.3 may be discharged more
effectively.
[0183] (Step S75)
[0184] In step S75, the valve 324 of the gas supply tube 320 is
opened to supply the NH.sub.3 into the processing chamber 201.
[0185] (Step S76)
[0186] The valve 324 of the gas supply tube 320 is closed to stop
the supply of the NH.sub.3 into the processing chamber 201. In this
case, the valve 243 of the gas exhaust pipe 231 is kept open to
exhaust the inside of the processing chamber 201 using the vacuum
pump 246 until the inner pressure of the processing chamber 201
reaches 20 Pa or less, and discharge the remaining the NH.sub.3
from the processing chamber 201. In this case, when an inert gas
such as N.sub.2 is supplied into the processing chamber 201, the
remaining the NH.sub.3 may be discharged more effectively.
[0187] A TiN film having a predetermined film thickness is formed
on the wafer 200 using many kinds of other CVD methods while
removing a gas in the processing chamber 201 by performing steps
S71 through S76 as one cycle once or a predetermined number of
times.
Eighth Embodiment
[0188] FIG. 18 shows a sequence according to an eighth embodiment.
In addition, FIG. 19 is a flow diagram illustrating a process
according to the eighth embodiment. Hereinafter the sequence
according to the eighth embodiment will now be described with
reference to FIGS. 18 and 19.
[0189] (Step S81)
[0190] In step S81, the valve 314 of the gas supply tube 310 is
opened to start the supply of the TiCl.sub.4.
[0191] (Step S82)
[0192] In step S82, the valve 314 of the gas supply tube 310 is
closed to stop the supply of the TiCl.sub.4 into the processing
chamber 201, and the valve 614 is opened to allow the TiCl.sub.4 to
flow into the vent line 610. In this case, the valve 243 of the gas
exhaust pipe 231 is kept open to exhaust the inside of the
processing chamber 201 using the vacuum pump 246 until the inner
pressure of the processing chamber 201 reaches 20 Pa or less, and
discharge the remaining the TiCl.sub.4 from the processing chamber
201. In this case, when an inert gas such as N.sub.2 is supplied
into the processing chamber 201, the remaining the TiCl.sub.4 may
be discharged more effectively.
[0193] (Step S83)
[0194] In step S83, the valve 324 of the gas supply tube 320 is
opened to supply the NH.sub.3 into the processing chamber.
[0195] (Step S84)
[0196] The valve 324 of the gas supply tube 320 is closed to stop
the supply of the NH.sub.3 into the processing chamber, and the
valve 614 is opened to allow the TiCl.sub.4 to flow into the vent
line 610. In this case, the valve 243 of the gas exhaust pipe 231
is kept open to exhaust the inside of the processing chamber 201
using the vacuum pump 246 until the inner pressure of the
processing chamber 201 reaches 20 Pa or less, and discharge the
remaining the NH.sub.3 from the processing chamber 201. In this
case, when an inert gas such as N.sub.2 is supplied into the
processing chamber 201, the remaining the NH.sub.3 may be
discharged more effectively.
[0197] (Step S85)
[0198] In step S85, the valve 314 of the gas supply tube 310 is
opened to start the supply of the TiCl.sub.4, and the valve 324 of
the gas supply tube 320 is opened to supply the NH.sub.3 into the
processing chamber 201.
[0199] (Step S86)
[0200] In step S86, the valve 314 of the gas supply tube 310 is
closed to stop the supply of the TiCl.sub.4 into the processing
chamber 201, and the valve 614 is opened to allow the TiCl.sub.4 to
flow into the vent line 610. Simultaneously, the valve 324 of the
gas supply tube 320 is closed to stop the supply of the NH.sub.3
into the processing chamber 201. In this case, the valve 243 of the
gas exhaust pipe 231 is kept open to exhaust the inside of the
processing chamber 201 using the vacuum pump 246 until the inner
pressure of the processing chamber 201 reaches 20 Pa or less, and
discharge the remaining the TiCl.sub.4 and the NH.sub.3 from the
processing chamber 201. In this case, when an inert gas such as
N.sub.2 is supplied into the processing chamber 201, the remaining
the TiCl.sub.4 and the NH.sub.3 may be discharged more
effectively.
[0201] (Step S87)
[0202] In step S87, the valve 324 of the gas supply tube 320 is
opened to supply the NH.sub.3 into the processing chamber 201.
[0203] (Step S88)
[0204] The valve 324 of the gas supply tube 320 is closed to stop
the supply of the NH.sub.3 into the processing chamber 201. In this
case, the valve 243 of the gas exhaust pipe 231 is kept open to
exhaust the inside of the processing chamber 201 using the vacuum
pump 246 until the inner pressure of the processing chamber 201
reaches 20 Pa or less, and discharge the remaining the NH.sub.3
from the processing chamber 201. In this case, when an inert gas
such as N.sub.2 is supplied into the processing chamber 201, the
remaining the NH.sub.3 may be discharged more effectively.
[0205] A TiN film having a predetermined film thickness is formed
on the wafer 200 using many kinds of other CVD methods while
removing a gas in the processing chamber 201 by performing steps
S81 through S88 as one cycle once or a predetermined number of
times.
[0206] In the above-described seventh and eighth embodiments, at
least one pulse of each of two or more pulses of the Ti source and
the N source flows simultaneously.
[0207] According to the seventh and eighth embodiments, since a CVD
reaction between the source gas and the modification gas is caused
by supplying the source gas and the modification gas
simultaneously, a higher film-forming rate may be achieved, compare
to the ALD reaction. In addition, after the source gas and the
modification gas are supplied separately or simultaneously, both or
either of the source gas and the modification gas to be supplied
next may effectively react with each other by stopping the supply
of a gas to remove products (the source gas, the modification gas,
and intermediates and byproducts thereof) remaining in the reaction
chamber. In addition, after the source gas and the modification gas
are supplied simultaneously, an ALD reaction between the
modification gas and the source gas deposited onto the substrate
may be caused to facilitate generation of byproducts (HCl, etc.) by
stopping the supply of both the source gas and the modification
gas, removing products (the source gas, the modification gas, and
intermediates and byproducts thereof) remaining in the reaction
chamber and exposing the substrate to only the modification gas,
the NH.sub.3. Therefore, effective removal of Cl in the film is
possible. Before the CVD reaction between the source gas, the
TiCl.sub.4, and the modification gas, the NH.sub.3, seed crystals
having a low Cl concentration may also be formed on the substrate
by exposing the substrate to only the source gas, the TiCl.sub.4,
to adsorb the source gas and intermediates thereof onto the
substrate during the ALD reaction. In addition, when the supply of
the source gas, the TiCl.sub.4, and the supply of the modification
gas, the NH.sub.3, are performed during two or more pulses in the
one cycle, the source gas and the modification gas are supplied
simultaneously during at least one pulse, and the source gas and
the modification gas are separately supplied during at least one
pulse. Therefore, effects such as improvement of the film-forming
rate caused by the CVD reaction (an effect obtained by supplying
the source gas and the modification gas simultaneously), formation
of the seed crystals having a low Cl concentration caused by the
ALD reaction (an effect obtained by supplying only the source gas)
and removal of Cl remaining in the film caused by the ALD reaction
(an effect obtained by supplying only the modification gas) may be
obtained.
[0208] According to the present invention, a TiN film that is
higher in quality than a TiN film formed only by the CVD method may
be provided at a higher film-forming rate, that is, with a higher
productivity than a TiN film formed only by the ALD method. In
addition, since a high-quality thin film may be formed at a low
temperature, a thermal budget may be increased.
[0209] Meanwhile, process conditions such as a temperature are not
intentionally changed during the processing. However, a pressure
may be suitably changed.
[0210] In addition, among the above-mentioned embodiments, the
TiCl.sub.4 may be first supplied to adsorb a source such as Ti onto
the substrate, and the TiCl.sub.4 and the NH.sub.3 may then be
supplied to react with the source, thereby forming a TiN film.
Finally, the NH.sub.3 may be supplied to modify the grown film.
[0211] In addition, the formed film may be nitrified by supplying
the NH.sub.3 in the last step.
[0212] In addition, A Ti seed may be attached to the substrate by
supplying the TiCl.sub.4 at the beginning.
[0213] In addition, a case where the first processing gas such as
the TiCl.sub.4 and the second processing gas such as the NH.sub.3
are supplied into the processing chamber 201 simultaneously has
been described, but the expression "supplying the first processing
gas and the second processing gas into a processing chamber
simultaneously" should be thought of as meaning that at least some
of supply times of respective gases overlap each other. More
particularly, when the first processing gas and the second
processing gas are supplied into the processing chamber, one
processing gas may be first supplied in one direction, and the
other processing gas may be continuously supplied in the other
direction even after the supply of the one processing gas is
stopped in the one direction. That is, the supply of the first
processing gas and the supply of the second processing gas into the
processing chamber may be performed or stopped at different time
points.
[0214] Meanwhile, although the vertical apparatus has been
generally illustrated as described above, the present invention is
not limited to the vertical apparatus, but the present invention
are also applicable to other apparatuses such as a single-type
apparatus to form a TiN film using the CVD method. In addition,
although the vertical thermal CVD apparatus has been generally
illustrated as described above, the present invention is not
limited to the vertical thermal CVD apparatus, but the present
invention are also applicable to other apparatuses such as a plasma
CVD apparatus and an optical CVD apparatus to form a TiN film using
the CVD method.
Preferred Embodiments of the Present Invention
[0215] Hereinafter, preferred embodiments of the present invention
will be now described in further detail.
[0216] (1) According to one embodiment of the present invention,
there is provided a method of manufacturing a semiconductor device
in which a film is formed on a substrate placed in a processing
chamber by reaction of a modification gas with a source gas. Here,
the method of manufacturing a semiconductor device includes a
source gas exposure process for exposing the substrate to the
source gas, and a modification gas exposure process for exposing
the substrate to the modification gas, wherein one round of the
source gas exposure process and two rounds of the modification gas
exposure processes are performed as one cycle repeatedly a
plurality of cycles.
[0217] (2) According to another embodiment of the present
invention, there is provided a method of manufacturing a
semiconductor device in which a film is formed on a substrate
placed in a processing chamber by reaction of a modification gas
with a source gas. Here, the method of manufacturing a
semiconductor device includes a film-forming process of forming a
film by exposing the substrate to the source gas and the
modification gas simultaneously, a removal process of removing an
atmosphere inside the processing chamber after the film-forming
process, and a modification process of modifying the film formed on
the substrate by exposing the substrate to the modification gas
after the removal process.
[0218] (3) Preferably, the film-forming process, the removal
process, and the modification process of (2) are performed as one
cycle repeatedly a plurality of cycles until a film having a
predetermined film thickness is formed on the substrate.
[0219] (4) Preferably, in the film-forming process of (2), a time
taken to expose the substrate to the source gas is different from a
time taken to expose the substrate to the modification gas.
[0220] (5) Preferably, in the film-forming process of (4), the time
it takes to expose the substrate to the modification gas is set to
a longer period than the time it takes to expose the substrate to
the source gas.
[0221] (6) Preferably, in the film-forming process of (5), a film
is deposited on the substrate by starting to expose the substrate
to the source gas and the modification gas simultaneously point,
and the film deposited on the substrate is modified by exposing the
substrate to only the modification gas.
[0222] (7) Preferably, in the film-forming process of (5), after
the substrate is exposed to only the modification gas, a film is
deposited on the substrate by exposing the substrate to the
modification gas and simultaneously exposing the substrate to the
source gas, and the film deposited on the substrate is modified by
exposing the substrate to only the modification gas.
[0223] (8) Preferably, in the film-forming process of (5), a film
is formed on the substrate by exposing the substrate to only the
source gas, and then exposing the substrate to the source gas and
simultaneously exposing the substrate to the modification gas, and
the substrate is then exposed to only the modification gas.
[0224] (9) Preferably, in the film-forming process of (2), at least
some of the source gas is adsorbed onto the substrate by exposing
the substrate to only the source gas, a film is then deposited onto
the substrate by reaction with the source gas while at least some
of the source gas adsorbed onto the substrate is being modified by
exposing the substrate to the modification gas while exposing the
substrate to the source gas, and the film deposited on the
substrate is subsequently modified by exposing the substrate to
only the modification gas.
[0225] (10) Preferably, in the film-forming process of (4), the
time it takes to expose the substrate to the source gas is set to a
longer period than the time it takes to expose the substrate to the
modification gas.
[0226] (11) Preferably, in the film-forming process of (10), after
the substrate is exposed to only the source gas, a film is formed
on the substrate by exposing the substrate to the modification gas
while exposing the substrate to the source gas, and the substrate
is subsequently exposed to only the source gas.
[0227] (12) Preferably, in the film-forming process of (10), at
least some of the source gas is adsorbed onto the substrate by
exposing the substrate to only the source gas, a film is then
deposited on the substrate by reaction with the source gas while at
least some of the source gas adsorbed onto the substrate is
modified by exposing the substrate to the modification gas while
exposing the substrate to the source gas, and at least some of the
source gas is subsequently adsorbed onto the substrate by exposing
the substrate to only the source gas.
[0228] (13) According to still another embodiment of the present
invention, there is provided a method of manufacturing a
semiconductor device in which a film is formed on a substrate
placed in a processing chamber by allowing a modification gas to
react with a source gas. Here, the method of manufacturing a
semiconductor device includes a deposition process of depositing a
film by exposing the substrate to the source gas and the
modification gas simultaneously, a removal process of removing an
atmosphere inside the processing chamber after the deposition
process, a modification process of modifying the film formed on the
substrate by exposing the substrate to the modification gas, and a
source adsorption process of adsorbing a source onto the substrate
by exposing the substrate to the source gas.
[0229] (14) Preferably, in (13), at least one round of the
deposition process, plural rounds of the removal process, at least
one round of the modification process and at least one round of the
source adsorption process are preformed as one cycle repeatedly a
plurality of cycles until a film having a predetermined film
thickness is formed on the substrate.
[0230] (15) According to yet another-embodiment of the present
invention, there is provided a method of manufacturing a
semiconductor device in which a film is formed on a substrate
placed in a processing chamber by allowing a modification gas to
react with a source gas. Here, the method of manufacturing a
semiconductor device includes a source gas exposure process of
exposing the substrate to the source gas, a film-forming process of
depositing a film while modifying the source gas adsorbed onto the
substrate by exposing the substrate to the modification gas while
exposing the substrate to the source gas after the source gas
exposure process, a modification process of modifying the film
deposited onto the substrate by exposing the substrate to the
modification gas in a state where the exposure of the substrate to
the source gas is stopped after the film-forming process, and a
removal process of removing an atmosphere inside the processing
chamber, wherein the source gas exposure process, the film-forming
process, the modification process, and the removal process are
performed in order repeatedly a predetermined number of times.
[0231] (16) According to yet another embodiment of the present
invention, there is provided a method of manufacturing a
semiconductor device in which a film is formed on a substrate
placed in a processing chamber by allowing a modification gas to
react with a source gas. Here, the method of manufacturing a
semiconductor device includes a modification gas exposure process
of exposing the substrate to the modification gas, a film-forming
process of exposing the substrate to the source gas while exposing
the substrate to the modification gas after the modification gas
exposure process, a source gas exposure process of exposing the
substrate to the source gas in a state where the exposure of the
substrate to the modification gas is stopped after the film-forming
process, and a removal process of removing an atmosphere inside the
processing chamber, wherein the modification gas exposure process,
the film-forming process, the source gas exposure process, and the
removal process are performed in order repeatedly a predetermined
number of times.
[0232] (17) Preferably, in the film-forming process of any of (2)
through (12), (15) and (16), the modification gas is activated and
the substrate is exposed thereto.
[0233] (18) Preferably, in the deposition process of (13) or (14),
the modification gas is activated and the substrate is exposed
thereto.
[0234] (19) Preferably, in (17) or (18), the modification gas is
activated by plasma excitation.
[0235] (20) Preferably, in (17) or (18), the modification gas is
activated by photo-excitation.
[0236] (21) Preferably, a semiconductor device manufactured using
any of (1) through (20) is provided.
[0237] (22) According to yet another embodiment of the present
invention, there is provided a substrate processing apparatus
including a processing chamber for accommodating a substrate, a
source gas supply system for supplying a source gas into the
processing chamber, a modification gas supply system for supplying
a modification gas into the processing chamber, an exhaust system
for exhausting an atmosphere inside the processing chamber, and a
control unit for controlling the source gas supply system, the
modification gas supply system, and the exhaust system, wherein the
control unit controls the source gas supply system, the
modification gas supply system, and the exhaust system to form a
film on the substrate by supplying the source gas and the
modification gas into the processing chamber simultaneously,
exhaust the atmosphere inside the processing chamber, and modify
the film formed on the substrate by supplying the modification gas
into the processing chamber.
[0238] (23) According to yet another embodiment of the present
invention, there are provided a film-forming method and a
film-forming apparatus for forming a TiN film on a substrate to be
processed in which a conductive film, an insulation film or a
conductive pattern separated by an insulation film is exposed by
allowing any of an inorganic metal compound or an organometallic
compound containing N (hereinafter, an N source) to react with any
of an inorganic metal compound or an organometallic compound
containing Ti (hereinafter, a Ti source), wherein the TiN film is
periodically formed on the substrate to be processed by supplying
the Ti source and the N source using a pulse.
[0239] (24) Preferably, in (23), one cycle of a film-forming
sequence is composed of one pulse of the Ti source and two or more
pulses of the N source.
[0240] (25) Preferably, in (23) or (24), when the N source flows
simultaneously with the Ti source, a pulse of the Ti source and
pulses of the N source are turned on simultaneously point, and the
pulses of the N source are turned off after the pulse of the Ti
source is turned off.
[0241] (26) Preferably, in (23) or (24), when the N source flows
simultaneously with the Ti source, the pulse of the Ti source is
turned on after the pulses of the N source are turned on, and the
pulses of the N source are turned off after the pulse of the Ti
source is turned off.
[0242] (27) Preferably, in (23) or (24), when the N source flows
simultaneously with the Ti source, the pulses of the N source are
turned on after the pulse of the Ti source is turned on, and the
pulses of the N source are turned off after the pulse of the Ti
source is turned off.
[0243] (28) Preferably, in (23) or (24), when the N source flows
simultaneously with the Ti source, the pulses of the N source are
turned on after the pulse of the Ti source is turned on, and the
pulse of the Ti source is turned off after the pulses of the N
source are turned off.
[0244] (29) Preferably, in (23), one cycle of a film-forming
sequence is composed of two or more pulses of the Ti source and two
or more pulses of the N source.
[0245] (30) Preferably, in (29), at least one pulse of each of the
pulses of the Ti source and the pulses of the N source is
configured to flow simultaneously during the one cycle of the
film-forming sequence.
[0246] (31) Preferably, in the one cycle of the film-forming
sequence of (23), there is a time zone at which the pulses of the
Ti source and the N source are in an ON state simultaneously, only
one of the pulses of the Ti source and the N source is in an ON
state.
[0247] (32) Preferably, in (31), the Ti source is first turned on
and the N source is then turned on, and the Ti source is turned off
and the N source is then turned off.
[0248] (33) Preferably, in (31), the Ti source is turned on after
the N source is turned on, and the N source is turned off after the
Ti source is turned off.
[0249] (34) Preferably, in any of (23) through (33), the Ti source
is titanium tetrachloride.
[0250] (35) Preferably, in any of (23) through (33), the N source
is ammonia.
[0251] (36) Preferably, in any of (23) through (33), plasma
application and light irradiation are performed at a time point
when the pulses of the Ti source and the N source are in an ON
state simultaneously.
[0252] (37) Preferably, there are provided a film-forming
apparatus, as the film-forming apparatus described in any one of
(23) through (36), which is a batch furnace that can process a
plurality of substrates to be processed simultaneously, and a
film-forming method using the film-forming apparatus.
[0253] (38) Preferably, there are provided a film-forming
apparatus, as the film-forming apparatus described in (37),
including a vertical furnace body having a shape where the
substrates to be processed are processed while overlapping each
other in plural numbers in a longitudinal direction, and an inner
tube arranged in a reaction tube and having nearly the same
diameter as the substrates to be processed, wherein a gas is
introduced and exhausted in a lateral direction between the
substrates to be processed arranged inside the inner tube, and a
film-forming method using the film-forming apparatus.
[0254] (39) Preferably, there are a single-type film-forming
apparatus, as the film-forming apparatus described in any one of
(23) through (36), that processes substrates to be processed one by
one, and a film-forming method using the film-forming
apparatus.
[0255] (40) According to yet another embodiment of the present
invention, there is provided a method of manufacturing a
semiconductor device including a substrate-loading process of
loading a substrate into a processing chamber, a film-forming
process of forming a predetermined film on the substrate by
supplying the first processing gas and the second processing gas
into the processing chamber simultaneously, a removal process of
stopping the supply of the first processing gas and the second
processing gas and removing the first processing gas and the second
processing gas remaining in the processing chamber, a modification
process of modifying the film formed on the substrate by supplying
the second processing gas into the processing chamber after the
removal process, and a substrate-unloading process of unloading the
substrate from the processing chamber, wherein, in the film-forming
process, a time taken to supply the second processing gas into the
processing chamber is longer than a time taken to supply the first
processing gas into the processing chamber.
[0256] (41) Preferably, in the film-forming process of (40), a film
is formed on the substrate by starting to supply the first
processing gas and the second processing gas into the processing
chamber simultaneously, and the film formed on the substrate is
then modified by supplying the second processing gas in a state
where the supply of the first processing gas is stopped.
[0257] (42) Preferably, in the film-forming process of (41), a film
is formed on the substrate by supplying the second processing gas
into the processing chamber in a state where the supply of the
first processing gas is stopped and subsequently supplying the
first processing gas into the processing chamber simultaneously
while supplying the second processing gas into the processing
chamber, and the film formed on the substrate is modified by
supplying the second processing gas into the processing chamber in
a state where the supply of the first processing gas is
stopped.
[0258] (43) Preferably, in the film-forming process of (41), a film
is formed on the substrate by supplying the first processing gas
into the processing chamber in a state where the supply of the
second processing gas is stopped and subsequently supplying the
second processing gas into the processing chamber while supplying
the first processing gas into the processing chamber, and the film
formed on the substrate is modified by supplying the second
processing gas into the processing chamber in a state where the
supply of the first processing gas is stopped.
[0259] (44) Preferably, in the film-forming process of (41), at
least some of the first processing gas is adsorbed onto the
substrate by supplying the first processing gas into the processing
chamber in a state where the supply of the second processing gas is
stopped, a film is then formed on the substrate by reaction with
the first processing gas while modifying at least some of the first
processing gas adsorbed onto the substrate by supplying the second
processing gas into the processing chamber while supplying the
first processing gas into the processing chamber, and the film
formed on the substrate is modified by supplying the second
processing gas into the processing chamber in a state where the
supply of the first processing gas is stopped.
[0260] (45) According to yet another embodiment of the present
invention, there is provided a method of manufacturing a
semiconductor device including a substrate-loading process of
loading a substrate into a processing chamber, a film-forming
process of forming a predetermined film on the substrate by
supplying the first processing gas and the second processing gas
into the processing chamber simultaneously, a removal process of
stopping the supply of the first processing gas and the second
processing gas and removing the first processing gas and the second
processing gas remaining in the processing chamber, a modification
process of modifying the film formed on the substrate by supplying
the second processing gas into the processing chamber, an
adsorption process of stopping the supply of the second processing
gas and adsorbing at least some of the second processing gas onto
the substrate by supplying the first processing gas into the
processing chamber, and a substrate-unloading process of unloading
the substrate from the processing chamber.
[0261] (46) Preferably, in (45), at least one round of the
film-forming process, plural rounds of the removal process, at
least one round of the modification process, and at least one round
of the adsorption process are performed as one cycle repeatedly a
plurality of cycles until a film having a predetermined film
thickness is formed on the substrate.
[0262] (47) According to yet another embodiment of the present
invention, there is provided a method of manufacturing a
semiconductor device including a substrate-loading process of
loading a substrate into a processing chamber, an adsorption
process of adsorbing a first element onto the substrate by
supplying the first processing gas containing the first element
into the processing chamber, a film-forming process of forming a
predetermined film on the substrate by reaction with the first
processing gas and the first element adsorbed onto the substrate by
supplying the second processing gas containing a second element
while supplying the first processing gas into the processing
chamber, a modification process of modifying the film formed on the
substrate by stopping the supply of the first processing gas and
supplying the second processing gas into the processing chamber, a
removal process of stopping the supply of the second processing gas
and removing the first processing gas and the second processing gas
remaining in the processing chamber, and a substrate-unloading
process of unloading the substrate from the processing chamber,
wherein the adsorption process, the film-forming process, the
modification process, and the removal process are performed in
order repeatedly a predetermined number of times.
[0263] (48) Preferably, in any of (40) through (47), the second
processing gas is activated and supplied into the processing
chamber.
[0264] (49) Preferably, in any of (40) through (47), the second
processing gas is a nitrogen-containing gas or an oxygen-containing
gas.
[0265] (50) Preferably, in (48), the second processing gas is
activated by plasma excitation.
[0266] (51) Preferably, in (48), the second processing gas is
activated by photo-excitation.
[0267] (52) According to yet another embodiment of the present
invention, there is provided a method of manufacturing a
semiconductor device including a first process of loading a
substrate into a processing chamber, a second process of supplying
the first processing gas into the processing chamber, a third
process of supplying the second processing gas into the processing
chamber while supplying the first processing gas into the
processing chamber, a fourth process of stopping the supply of the
first processing gas and supplying the second processing gas, a
fifth process of stopping the supply of the second processing gas
and removing the first processing gas and the second processing gas
remaining in the processing chamber, and a sixth process of
unloading the substrate from the processing chamber, wherein the
first process through the sixth process are performed in order
repeatedly a predetermined number of times.
[0268] (53) Preferably, a semiconductor manufactured by the method
described in any of (40) through (52) is provided.
[0269] (54) According to yet another embodiment of the present
invention, there is provided a substrate processing apparatus
including a processing chamber for accommodating a substrate; the
first processing gas supply means for supplying the first
processing gas into the processing chamber; the second processing
gas supply means for supplying the second processing gas into the
processing chamber; an exhaust means for exhausting an inside of
the processing chamber; and
[0270] a control unit for controlling the first processing gas
supply means, the second processing gas supply means, and the
exhaust means to form a film on the substrate by supplying the
first processing gas and the second processing gas into the
processing chamber simultaneously, exhaust the first processing gas
and the second processing gas remaining in the processing chamber
by stopping the supply of the first processing gas and the second
processing gas, and modify the film formed on the substrate by
supplying the second processing gas into the processing chamber,
wherein, when the first processing gas and the second processing
gas are supplied into the processing chamber simultaneously, the
control unit is configured to control the first processing gas
supply means and the second processing gas supply means so that a
time taken to supply the second processing gas into the processing
chamber is longer than a time taken to supply the first processing
gas into the processing chamber.
* * * * *