U.S. patent application number 12/208143 was filed with the patent office on 2009-01-08 for substrate processing method.
This patent application is currently assigned to TOKYO ELECTRON LIMITED. Invention is credited to Gishi CHUNG, Yoshihisa KAGAWA, Yusaku KASHIWAGI, Yasuhiro OSHIMA.
Application Number | 20090011149 12/208143 |
Document ID | / |
Family ID | 34575955 |
Filed Date | 2009-01-08 |
United States Patent
Application |
20090011149 |
Kind Code |
A1 |
KASHIWAGI; Yusaku ; et
al. |
January 8, 2009 |
SUBSTRATE PROCESSING METHOD
Abstract
A method of forming a low-K dielectric film, comprises the steps
of placing a substrate carrying thereon a low-K dielectric film on
a stage, heating the low-K dielectric film on the stage, processing
the low-K dielectric film by plasma of a processing gas containing
a hydrogen gas, the plasma being excited while supplying the
processing gas over the low-K dielectric film, wherein the plasma
is excited within 90 seconds after placing the substrate upon the
stage.
Inventors: |
KASHIWAGI; Yusaku;
(Amagasaki-Shi, JP) ; OSHIMA; Yasuhiro;
(Amagasaki-Shi, JP) ; KAGAWA; Yoshihisa;
(Yokohama-shi, JP) ; CHUNG; Gishi; (Nirasaki-shi,
JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
TOKYO ELECTRON LIMITED
Minato-ku
JP
|
Family ID: |
34575955 |
Appl. No.: |
12/208143 |
Filed: |
September 10, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11431720 |
May 11, 2006 |
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12208143 |
|
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PCT/JP04/16541 |
Nov 8, 2004 |
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11431720 |
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Current U.S.
Class: |
427/578 ;
134/1.1; 257/E21.26 |
Current CPC
Class: |
H01L 21/02126 20130101;
H01L 21/0234 20130101; C23C 16/56 20130101; C23C 16/401 20130101;
H01L 21/3121 20130101 |
Class at
Publication: |
427/578 ;
134/1.1 |
International
Class: |
B01J 19/08 20060101
B01J019/08; C25F 3/00 20060101 C25F003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 11, 2003 |
JP |
2003-381591 |
Dec 16, 2003 |
JP |
2003-417896 |
Claims
1. A method of cleaning a processing vessel used for forming an
insulation film containing Si and C on a substrate to be processed,
by removing said insulation film from an inner wall of said
processing vessel, comprising the steps of: exciting first plasma
of a first processing gas containing oxygen in said processing
vessel; and exciting second plasma of a second processing gas
containing fluorine in said processing vessel.
2. The method as claimed in claim 1, wherein said step of exciting
said first plasma and said step of exciting said second plasma are
conducted repeatedly for plural times.
3. The method as claimed in claim 2, wherein said step of exciting
said first plasma and said step of exciting said second plasma are
conducted concurrently.
4. The method as claimed in claim 1, wherein said step of exciting
said first plasma and said step of exciting said second plasma are
conducted by using a parallel-plate plasma processing apparatus or
a microwave plasma processing apparatus having a radial line slot
antenna.
5. A substrate processing method, comprising the steps of: forming,
in a processing vessel, an insulation film containing Si and C on a
substrate to be processed; and cleaning said processing vessel
after said step of forming said insulation film, wherein said step
of cleaning said processing vessel comprises: a first step of
exciting plasma of a first processing gas containing oxygen in said
processing vessel; and a second step of exciting plasma of a second
processing gas containing fluorine in said processing vessel.
6. The method as claimed in claim 5, wherein said second step is
conducted after said first step.
7. The method as claimed in claim 5, wherein said first step and
said second step are conducted plural times repeatedly.
8. The method as claimed in claim 5, wherein said first step and
said second step are conducted concurrently.
9. The method as claimed in claim 5, wherein said insulation film
is formed by a plasma CVD process that uses an organic silane
gas.
10. The method as claimed in claim 5, wherein said first step and
said second step are conducted by using a parallel-plate plasma
processing apparatus or a microwave plasma processing apparatus
having a radial line slot antenna.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a division of and claims the
benefit of priority from U.S. Ser. No. 11/431,720, filed on May 11,
2006, which is a continuation application filed under 35 U.S.C.
111(a) claiming benefit under 35 U.S.C. 120 and 365(c) of PCT
application PCT/JP2004/016541, field on Nov. 8, 2004, which is
based on Japanese priority applications 2003-381591, filed on Nov.
11, 2003 and 2003-417896, filed on Dec. 16, 2003, the entire
contents of each are incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention generally relates to the art of
substrate processing and more particularly to a substrate
processing method used for forming an insulation film in the
fabrication process of a semiconductor device.
[0003] With increase of performance in recent semiconductor
devices, there arises a situation with such recent high-speed
semiconductor devices that use a multilayer interconnection
structure in that interconnection patterns in the multilayer
interconnection structure are disposed close with each other as a
result of device miniaturization. Associated with this, there is
caused a problem of wiring delay by the parasitic capacitance
formed between these interconnection patterns. Such parasitic
capacitance changes in inverse proportion to the distance between
the interconnection patterns and is proportional to the specific
dielectric constant of the insulation film existing between the
interconnection patterns.
[0004] Thus, in order to solve the problem of wiring delay in the
multilayer interconnection structure and to decrease the parasitic
capacitance therein, investigations are being made to use a
material of low specific dielectric constant (low-K) in the
multilayer interconnection structure for the interlayer insulation
film.
[0005] The specific dielectric constant of a CVD-SiO.sub.2 film
that has been used conventionally as an interlayer insulation film
is about 3.5-4. Thus, in order to decrease the specific dielectric
constant further, it is practiced in the art to add fluorine to the
CVD-SiO.sub.2 film to form a SiOF film. With this approach,
however, it is difficult to attain the specific dielectric constant
of lower than the 3.3-3.5, while this degree of decrease of the
specific dielectric constant is not sufficient for recent
high-density semiconductor integrated circuit devices, and there
are cases in which necessary operational speed is not attained.
[0006] Thus, there is proposed an insulation film of further lower
dielectric constant formed by plasma CVD process with the use of
organic silane gas or an insulation film formed by SOD
(spin-on-deposition) process, to provide a so called low-K
interlayer insulation film. Further, there is proposed a porous
film, in which any of these films are made porous. Thus, intensive
efforts are being made to develop a low-K interlayer insulation
film having a specific dielectric constant of 2.5 or less.
[0007] It should be noted that an insulation film formed by a
plasma CVD process has a large dielectric constant immediately
after the film formation process thereof, and thus, there are cases
in which it becomes necessity to reduce the specific dielectric
constant by way of predetermined processing such as plasma
processing, or the like. Further, such low-K insulation film formed
by a plasma CVD process tends to suffer from the problem of poor
mechanical strength, and there are cases it is necessary to improve
the mechanical strength by way of predetermined processing.
REFERENCES
[0008] Patent Reference 1 United States Patent Application
Publication 2001/0030369 official gazette
[0009] Patent Reference 2 United States Patent Application
Publication 2002/0055275 official gazette
[0010] Patent Reference 3 British Patent 2,361,808
[0011] Patent Reference 4 WO00/51174 official gazette
[0012] Patent Reference 5 WO01/01472 official gazette
SUMMARY OF THE INVENTION
[0013] However, there still remain the cases in which mechanical
strength of the film is insufficient even when the insulation film
formed by a plasma CVD process is applied subsequently with such
predetermined processing for reducing the dielectric constant, and
there have been cases in which it is difficult to achieve the
desired low dielectric constant and large mechanical strength at
the same time in an insulation film.
[0014] Accordingly, it is an object of the present invention to
provide a novel and useful film formation method wherein the
foregoing problems are eliminated.
[0015] A more specific object of the present invention is to
provide a film formation process capable of decreasing the
dielectric constant of an insulation film deposited by a plasma CVD
process while using an organic silane gas and at the same time
capable of improving the mechanical strength thereof.
[0016] According to a first aspect of the present invention, there
is provided a method of forming a low-K dielectric film, comprising
the steps of:
[0017] placing a substrate carrying thereon a low-K dielectric film
on a stage;
[0018] heating said low-K dielectric film on said stage;
[0019] processing said low-K dielectric film by plasma of a
processing gas containing a hydrogen gas, said plasma being excited
while supplying said processing gas over said low-K dielectric
film;
[0020] wherein said plasma is excited within 90 seconds after
placing said substrate upon said stage.
[0021] According to a second aspect of the present invention, there
is provided a method of cleaning a processing vessel used for
forming an insulation film containing Si and C on a substrate to be
processed, by removing said insulation film from an inner wall of
said processing vessel, comprising the steps of:
[0022] exciting first plasma of a first processing gas containing
oxygen in said processing vessel; and
[0023] exciting second plasma of a second processing gas containing
fluorine in said processing vessel.
[0024] According to a third aspect of the present invention, there
is provided a substrate processing method, comprising the steps
of:
[0025] forming, in a processing vessel, an insulation film
containing Si and C on a substrate to be processed; and
[0026] cleaning said processing vessel after said step of forming
said insulation film, wherein said step of cleaning said processing
vessel comprises:
[0027] a first step of exciting plasma of a first processing gas
containing oxygen in said processing vessel; and
[0028] a second step of exciting plasma of a second processing gas
containing fluorine in said processing vessel.
[0029] According to a fourth aspect of the present invention, there
is provided a method of forming a low-K dielectric film, comprising
the steps of:
[0030] forming a low-K dielectric film on a substrate by exciting
first plasma of a first processing gas containing an organic silane
gas; and
[0031] processing said low-K dielectric film by exciting second
plasma of a processing gas containing a hydrogen gas, said second
plasma being excited by supplying a second processing gas
containing a hydrogen gas to a space over said substrate where said
second plasma is to be excited,
[0032] wherein said second plasma has an electron temperature of
0.7-2 eV,
[0033] said low-K dielectric film having a decreased specific
dielectric constant after said step of processing said low-K
dielectric film with said second plasma.
[0034] According to the present invention, it becomes possible to
decrease the dielectric constant and improve the mechanical
strength of the insulation film formed by using an organic silane
gas.
[0035] Other objects and further features of the present invention
will become apparent from the following detailed description when
read in conjunction with attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0036] FIG. 1 is a flowchart showing a substrate processing method
according to first embodiment of the present invention;
[0037] FIG. 2 is a diagram showing an example of the substrate
processing apparatus used for substrate processing in the first
embodiment;
[0038] FIG. 3 is a first diagram showing the cross-sectional view
of the processing vessel used with the substrate processing
apparatus of FIG. 2 schematically;
[0039] FIG. 4 is a second diagram showing the cross-sectional view
of the processing vessel used with the substrate processing
apparatus of FIG. 2 schematically;
[0040] FIG. 5 is a flowchart showing the details of plasma
processing in the substrate processing method of FIG. 1;
[0041] FIG. 6 is a diagram showing the relationship between the
substrate temperature at the time of the plasma processing and the
specific dielectric constant of the insulation film;
[0042] FIG. 7A is a diagram showing a change of the specific
dielectric constant of the insulation film for the case in which
the time after placement of the substrate in the processing
apparatus to the excitation of the plasma is changed variously;
[0043] FIG. 7B is a diagram showing a change rate of film thickness
of the insulation film for the case in which the time after
placement of the substrate in the processing apparatus to the
excitation of the plasma is changed variously;
[0044] FIG. 8 is a cross-sectional view showing the processing
vessel used for the plasma processing schematically;
[0045] FIG. 9 is a plan view diagram showing an antenna plate used
with the processing vessel of FIG. 8;
[0046] FIG. 10A is a diagram showing a change of elastic modulus of
the insulation film for the case of changing the pressure in the
processing vessel;
[0047] FIG. 10B is a diagram showing the change of specific
dielectric constant of the insulation film for the case of changing
the pressure of the processing vessel;
[0048] FIG. 11 is a diagram showing the relationship between the
specific dielectric constant and elastic modulus of the insulation
film after the plasma processing;
[0049] FIG. 12 is a diagram showing the relationship between the
specific dielectric constant and elastic modulus of the insulation
film for the case of changing the distance between the microwave
transmission window and substrate to be processed;
[0050] FIG. 13 is a diagram schematically showing an example of
possible substrate processing apparatus capable of conducting the
substrate processing method according to a third embodiment of the
present invention;
[0051] FIG. 14 is a flowchart showing the substrate processing
method according to the third embodiment; and
[0052] FIGS. 15-18 are flowcharts showing the details of the
cleaning processing of the substrate processing method shown in
FIG. 14.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0053] Next, the present invention will be explained for preferred
embodiments with reference to the drawings.
FIRST EMBODIMENT
[0054] FIG. 1 is a diagram showing the flowchart of a substrate
processing method according to a first embodiment of the present
invention.
[0055] Referring to FIG. 1, a substrate processing is started with
a step 100 (designated as S100 in the drawing: similar designation
will be used throughout the drawings), and an insulation film is
deposited on the substrate to be processed in a step 200 while
using a first processing vessel to be described later. In the
present case, an insulation film (a SiCO(H) film) is formed on the
substrate to be processed by a plasma CVD process by introducing a
first processing gas containing an organic silane gas, such as a
trimethyl silane (SiH(CH.sub.3).sub.3) gas, as a first processing
gas and further by exciting plasma.
[0056] Next, in a step 300, the substrate thus formed with the
insulation film is transported from the first processing vessel to
a second processing vessel to be described later. Thereby, it
should be noted that the transportation is carried out by a
transportation arm of a vacuum transportation vessel to be
described later.
[0057] Next, in a step 400, plasma processing is conducted in the
second the processing vessel for improving mechanical strength and
further for reducing the specific dielectric constant of the
insulation film thus formed on the substrate.
[0058] In this process, the plasma excitation process is conducted
for example by introducing a hydrogen gas into the second
processing vessel as the second processing gas, and as a result of
the plasma processing of the insulation film, excess alkyl group
(--CHx) and excess hydroxyl group (--OH) in the insulation film are
removed and the specific dielectric constant of the insulation film
is reduced. At the same time, the mechanical strength of the
insulation film is improved and the film quality is improved.
[0059] The substrate processing is completed with a step 500.
[0060] It should be noted that the insulation film thus formed on
the substrate has a relatively high specific dielectric constant of
about 4 immediately after formation thereof in the first processing
vessel with the step 200, while the insulation film of this
specific dielectric constant is insufficient for a low-K interlayer
insulation film used for high-speed semiconductor devices.
[0061] Thus, in order to decrease the specific dielectric constant
of the insulation film and to improve the film quality such as the
mechanical strength of the insulation film, the process of FIG. 1
carries out a post-processing process including a plasma
processing, by introducing a hydrogen gas into the second
processing vessel.
[0062] Further, in the case of forming the film on the substrate to
be processed, it should be noted that the temperature of the
substrate is set to 100.degree. C. or less, typically at the room
temperature, while in the case of the plasma processing of the
insulation film thus formed, it is preferable to set the
temperature of the substrate to 350.degree. C. or more.
[0063] Thus, in the case of conducting the plasma processing after
the film formation process conducted in the first processing vessel
by using the same first processing vessel, there is a need of
elevating the temperature of the substrate to be processed, while
such a step of elevating the substrate temperature requires a
substantial time. Thus, it is practically not possible or realistic
to conduct the plasma processing of the insulation film formed by
the film formation processing in the first processing vessel, by
using the same first processing vessel and by elevating the
substrate temperature therein.
[0064] On the other hand, when the plasma processing is conducted
after the film formation processing in the first processing vessel
by transporting the substrate to the second processing vessel as in
the case of the present embodiment, it becomes possible to carry
out the substrate processing efficiently by elevating the
temperature of the stage that holds the substrate to be processed
in the second processing vessel to the predetermined substrate
temperature beforehand.
[0065] Also, this approach of the present embodiment of separating
the processing vessel for the film formation and the processing
vessel for the plasma processing is preferable in view of the
optimizing the timing of the temperature elevation and plasma
excitation for achieving the desired decrease of specific
dielectric constant of the insulation film as will be explained
later. Such optimized plasma processing method will be described
later.
[0066] Next, the substrate processing apparatus used for carrying
out the substrate processing shown in FIG. 1 will be explained with
reference to FIGS. 2-4.
[0067] FIG. 2 is a plan view diagram showing a substrate processing
apparatus 100 used with the present embodiment for carrying out the
substrate processing shown in FIG. 1 schematically.
[0068] Referring to FIG. 2, the substrate processing apparatus 100
includes a vacuum transportation chamber 101 including therein a
movable transportation arm 102, wherein the substrate processing
apparatus 100 further includes a processing chamber 200 used as the
first processing vessel for the film formation of the insulation
film on the substrate to be processed, a processing chamber 300
used as the second processing vessel for the plasma processing of
the insulation film, and load-lock chambers 103 and 104, such that
the processing chambers 200, 300 and the load-lock chambers 103 and
104 are coupled to the vacuum transportation chamber 101.
[0069] Further, there is provided an evacuation means not
illustrated in the processing chamber 200, the processing chamber
300, the vacuum transportation chamber 101, the load-lock chamber
103 and the load-lock chamber 104 for evacuating the interior
thereof to a depressurized state.
[0070] Thereby, it should be noted that the processing chamber 200,
the processing chamber 300, the load-lock chamber 103 and the
load-lock chamber 104 are connected to the vacuum transportation
chamber 101 via the gate valves 101c, 101d, 101a and 101b
respectively, and the foregoing gate valves are opened in the event
of transporting the substrate to be processed therethrough.
[0071] In the load-lock chambers 103 and 104, there are provided
doors 103a and 104a respectively. Thus, by opening the door 103a,
it becomes possible to load a wafer cassette C1 holding therein
plural substrates to be processed into the load-lock chamber 103.
Similarly, by opening the door 103b, it becomes possible to load a
wafer cassette C2 holding therein plural substrates to be processed
into the load-lock chamber 104.
[0072] In the case of carrying out the foregoing substrate
processing with the substrate processing apparatus 100, a substrate
W0 to be processed is transported to the processing chamber 200
from the cassette C1 or C2 via the vacuum transportation chamber
101 by way of the transportation arm 102, wherein the substrate
finished with the film formation processing in the processing
chamber 200 is transported to the processing chamber 300 through
the vacuum transportation chamber 101 by way of the transportation
arm 102. Further, the substrate finished with the plasma processing
in the processing chamber 300 is returned to the cassette C1 again.
Alternatively, it is stored in the cassette C2 of the load-lock
chamber 104.
[0073] Further, while FIG. 2 shows an example of using two
processing vessels connected to the vacuum transportation chamber,
it is also possible to connect more processing vessels to surfaces
101A or 101B of the vacuum transportation chamber 101 to form a
multi-chamber system.
[0074] Further, it should be noted that the operation of the
substrate processing apparatus 100 corresponding to the substrate
processing shown in the flowchart of the FIG. 1 is controlled by a
control means 100A that includes a storage medium and a computer
(CPU). For example, the operation such as loading of the substrate
to be processed, processing in the processing vessel, unloading of
the substrate after the processing, or the like, is controlled by
the control means 100A. Thereby, the operation of the control means
100A is controlled by a program stored in the storage medium.
[0075] Next, explanation will be made with regard to the processing
chamber 200 and the processing chamber 300.
[0076] FIG. 3 is a cross-sectional diagram showing the construction
of the processing chamber 200 schematically.
[0077] Referring to FIG. 3, the processing chamber 200 includes a
processing vessel 201 of aluminum or aluminum alloy and a stage
201A provided inside the processing vessel 201 for holding a
substrate Wf to be processed thereon. Thereby, a heater 201a is
embedded inside the stage 201A, and with this, the stage 201A can
heat the substrate Wf held thereon.
[0078] It should be noted that the interior of the processing
vessel 201 is evacuated by an evacuation means 205 such as a vacuum
pump connected to the processing vessel 201. Further, a shower head
201B is provided on the top part of the processing vessel 201 and a
first processing gas containing trimethyl silane is supplied from a
gas line 202 to the processing vessel 201 via the shower head 201B
by opening a valve 202A provided to the gas line 202.
[0079] Further, a high frequency power supply 204 is connected to
the shower head 201B electrically via a power supply line 203, and
it becomes possible to excite high frequency plasma in the
processing vessel 201 by supplying the high frequency electric
power to the shower head 201B. Here, it should be noted that the
shower head 201B and the processing vessel 201 are insulated be by
an insulation component 207 and the gas line 202 and the shower
head 201B are insulated by an insulation component 208.
[0080] In FIG. 3, illustration of the substrate in/out opening
provided in the processing vessel 201 in correspondence to the gate
valve 101c is omitted.
[0081] Formation of the insulation film on the substrate Wf in the
processing chamber 200 is conducted as follows.
[0082] First, the valve 202A is opened and an organic silane gas
such as a trimethyl silane gas, an oxygen gas and an inert gas such
as an Ar gas are supplied to the processing vessel 201 via the gas
line 202 connected to respective gas sources not illustrated with
respective flow rates of 100 sccm, 100 sccm and 600 sccm as the
first processing gas. Further, the pressure in the processing
vessel 201 is set to 100 Pa.
[0083] Next, a high frequency electric power of 250 W is supplied
to the shower head 201B from the high frequency power supply 204
and high frequency plasma is excited inside the processing vessel
201. In the present embodiment, the frequency of 27 MHz is used,
while it is possible and preferable to use the frequency of 13-60
MHz for the high frequency power.
[0084] Further, it is preferable to set the temperature of the
substrate to be processed Wf to 100.degree. C. or less, wherein the
present embodiment uses the substrate temperature of 25.degree. C.
(room temperature).
[0085] Here, there is caused a decomposition reaction of the
processing gas by the plasma thus excited, and deposition of an
insulation film takes place on the substrate, wherein the
insulation film thus deposited has the composition of SiCO(H) and a
specific dielectric constant of 3-4.
[0086] Next, the substrate carrying the insulation film thus formed
is transported to the processing chamber 300 for post-processing
wherein the post-processing converts the insulation film into a
low-K insulation film.
[0087] FIG. 4 shows the construction of the processing chamber 300
schematically.
[0088] Referring to FIG. 4, it will be noted that the processing
chamber 300 includes a processing vessel 301, a stage 301A, a
heater 301a, a shower head 301B, insulation components 307 and 308,
a gas line 302, a valve 302A, a power supply line 303, a high
frequency power supply 304 and an evacuation means 305 wherein the
processing vessel 301, the stage 301A, the heater 301a, the shower
head 301B, the insulation components 307 and 308, the gas line 302,
the valve 302A, the power supply line 303, the high frequency power
supply 304 and the evacuation means 305 have respective
constructions similar to those of the processing vessel 201, the
stage 201A, the heater 201a, the shower head 201B, the insulation
components 207 and 208, the gas line 202, the valve 202A, the power
supply line 203, the high frequency power supply 204 and the
evacuation means 205 and the description thereof will be
omitted.
[0089] In the processing chamber 300 of FIG. 4, it should be noted
that the gas line 302 is connected to a gas supply source of
hydrogen, and thus, the chamber 302 is supplied with a hydrogen gas
via the gas line 302.
[0090] The substrate formed with the insulation film in the
processing chamber 200 is transported to the processing chamber 300
through the vacuum transportation chamber 101, and the insulation
film of low dielectric constant is formed with the
post-processing.
[0091] Next, details of the plasma processing including the
post-processing carried out with the processing chamber 300 will be
explained with reference to the flowchart shown in FIG. 5.
[0092] FIG. 5 is a flowchart showing the process of the
post-processing carried out with the processing chamber 300.
[0093] Referring to FIG. 5, the gate valve 101d is opened with a
step 101, and the substrate formed with the insulation film is
transported to the processing chamber 300 from the processing
chamber 200 via the vacuum transportation chamber 101. Thereby, the
substrate is taken up by the transportation arm 102 and transported
to the stage 301A of the processing vessel 301.
[0094] Next, in a step 102, the substrate is placed upon the stage
301A.
[0095] In more detail, there are provided lifter pins on the stage
301A in a manner movable up and down, and the substrate held by the
transportation arm is unloaded upon lifter pins set to an elevated
position, wherein the substrate thus landed upon the lifter pins is
subsequently lowered and seated upon the stage 301A by lowering the
lifter pins.
[0096] Further, the stage 301A is heated to a predetermined
temperature by energizing the heater 301a embedded in the stage
301A, and thus, the substrate is held to a substrate temperature of
200-500.degree. C., preferably 300-400.degree. C. on the stage
301A.
[0097] Next, the valve 302A is opened in the step 104, and the
hydrogen gas is introduced into the processing vessel 301 from the
line 302 with a flow rate of 100-2000 sccm.
[0098] Next, in the step 105 (plasma ignition), the high frequency
power is supplied to the shower head 301B from the high frequency
power supply 304 with the electric power of 500-2000 W, such as
1500 W, and there is caused plasma excitation of hydrogen gas in
the processing vessel 301. In the present embodiment, a frequency
of 27 MHz is used for the high frequency, while it is possible and
preferable to use the frequency in the range of 13.56 MHz-60 MHz
for this purpose.
[0099] In the plasma process conducted in the procession vessel
301, it is preferable to conduct the plasma processing not
exceeding 90 seconds after the substrate is placed upon the stage
301A. With the process thereafter, the insulation film is converted
to a low-K film as a result of thermal energy and plasma
energy.
[0100] Next, in the step 106, a hydrogen plasma processing is
applied to the insulation film for 5 minutes, for example, and
application of the high frequency electric power is stopped with
step 107. Further, supply of the gas is terminated, and with this,
the processing is finished.
[0101] FIG. 6 shows the relationship between the specific
dielectric constant of the insulation film formed by the substrate
processing method of the present embodiment and the temperature of
the substrate at the time of the plasma processing.
[0102] Referring to FIG. 6, it can be seen that the dielectric
constant of the insulation film is decreased when the temperature
of the substrate at the time of the plasma processing is increased.
This indicates that the effect of removal of the hydroxyl group
(--OH) or organic material in the insulation film by the hydrogen
plasma (hydrogen ions and hydrogen radicals formed by plasma) is
enhanced with increase of the temperature of the plasma
processing.
[0103] On the other hand, when the temperature of the substrate is
elevated in the state where there is caused no plasma excitation,
there can be a case in which the reduction of specific dielectric
constant of the insulation film is not attained sufficiently even
when a plasma processing is applied subsequently.
[0104] For example, when the substrate is left for a long time on
the stage at an elevated substrate temperature before exciting the
plasma, there occurs a contraction in the insulation film, and
subsequent increase in the specific dielectric constant. When this
occurs, no satisfactory decrease of dielectric constant is attained
for the insulation film even when the plasma processing is
conducted thereafter.
[0105] FIG. 7A shows the specific dielectric constant of the
insulation film in the substrate processing method shown in FIG. 5
for the case the duration from the event of placing the substrate
on the stage in correspondence to the step 102 to the event of
plasma excitation (plasma ignition) corresponding to the steps 105
and 106 is changed variously.
[0106] Referring to FIG. 7A, it can be seen that the specific
dielectric constant of the insulation film is increased with
holding time from the event of placing the substrate to be
processed on the stage to the event of plasma excitation. For
example, it will be noted that a specific dielectric constant of
2.24 is obtained in the case when the holding time is 10 seconds,
while in the case the holding time is set to 60 seconds, the
specific dielectric constant is increased to 2.38.
[0107] Thus, it is possible to reduce the specific dielectric
constant of the insulation film by minimizing the holding time of
the substrate, in other words, the interval from the event of
placing the substrate to be processed on the stage to the event of
plasma excitation. More specifically, by setting the holding time
to be 90 seconds or less, it can be seen from FIG. 7A that the
specific dielectric constants of the insulation films is decreased
to 2.5 or less. Further, it becomes possible to attain the specific
dielectric constants of the insulation films of 2.3 or less, by
setting the holding time to be 30 seconds or less.
[0108] FIG. 7B shows the rate of change of the film thickness of
the insulation film (contraction rate) after the plasma processing,
for the case of changing the holding time similarly to the case of
FIG. 7A.
[0109] Referring to FIG. 7B, it can be seen that, while there is a
variation in the numerical values, there is a tendency that the
decrease of film thickness of the insulation film becomes large
when the holding time from the event of placing the substrate to be
processed upon the stage to the event of plasma excitation is
increased.
[0110] For example, in the case the holding time is 10 seconds, it
can be seen that the change rate of the film thickness is -3.0%
(3.0%, in terms of decrease rate of the film thickness), while in
the case where the holding time is 60 seconds, the change rate of
the film thickness becomes -7.0% (7.0%, in terms of decrease rate
of the film thickness). Thereby, the decrease rate of film
thickness is increased.
[0111] It is believed that this increase of density of the
insulation film reflects a polymerization reaction taking place in
the insulation film, while this polymerization reaction is believed
to be caused as a result of high temperature of the insulation film
caused by the fact that the substrate is left on the stage of high
temperature over a long time period. With this increase of the
density, there should be caused increase of dielectric constant of
the insulation film.
[0112] On the other hand, in order to decrease the dielectric
constant of the insulation film by the hydrogen plasma processing,
it is necessary to heat the substrate to a high temperature of
typically 300.degree. C. or more, preferably 340.degree. C. or
more, as noted before.
[0113] From this, it is clear that it is necessary to elevate the
temperature of the substrate to be processed to 350.degree. C. or
more in order to decrease the specific dielectric constant of the
insulation film to 2.5 or less, while it is preferable to cause
plasma excitation at the same time under the foregoing processing
condition that can reduce the dielectric constant of the insulation
film.
[0114] Thus, when the hydrogen plasma is not excited at the time of
elevating the temperature of the substrate to be processed, there
would be caused polymerization in the insulation film, leading to
increase of the film density and hence the dielectric constant.
[0115] Thus, it is preferable to excite the hydrogen plasma
promptly when the temperature of the substrate to be processed is
elevated, such that the plasma process is started before
substantial commencement of such polymerization process takes
place. It is thus preferable to carry out the substrate processing
that modifies the film quality by the active hydrogen (H+, H*)
formed as a result of the hydrogen plasma excitation, such that the
reaction causing the decrease of the dielectric constant by
removing therefrom excess OH group or alkyl group such as CH.sub.3
becomes predominant in the insulation film.
[0116] By using the low-K insulation film of the present embodiment
having the specific dielectric constant of 2.5 or less for the
interlayer insulation film of a semiconductor device, for example,
it is possible to reduce the parasitic capacitance between the
wiring patterns and the effect of wiring delay can be reduced.
Thus, the present embodiment is useful as the interlayer insulation
film of the semiconductor devices of high operational speed.
[0117] While the present embodiment has been explained for the
example that uses trimethyl silane as the organic silane gas, the
present invention is not limited to this particular example and it
is also possible to use other organic silane gas such as dimethyl
dimethoxy silane (DMDMOS).
[0118] For example, it is possible to introduce the first
processing gas formed of an organic silane such as dimethyl
dimethoxy silane, oxygen and an inert gas such as Ar with
respective flow rates of 100 sccm, 100 sccm and 150 sccm into the
processing vessel 201 and supply a high frequency power to the
shower head 201B with the electric power 250 W and from the high
frequency power supply 204 while setting the pressure inside the
processing vessel 201 to 60 Pa, such that high frequency plasma is
excited in the processing vessel 201. After the processing, a
similar process in the case of using trimethyl silane may be
conducted.
[0119] Thus, in the case of using dimethyl dimethoxy silane for the
organic silane gas, too, it is possible to obtain the effect
similar to the case of using trimethyl silane as explained
previously in the present embodiment.
[0120] The insulation film formed with the present embodiment shows
a modulus of longitudinal elasticity (Young modulus), which is one
of the elastic modula providing an index of mechanical strength, of
9.4 GPa in the case the film thickness of the insulation film is
200 nm and the specific dielectric constant is 2.3. In the case the
film thickness is 350 nm and the specific dielectric constant is
2.23, the modulus of longitudinal elasticity become 8.3 GPa.
[0121] Thereby, the modulus of longitudinal elasticity takes a
value of 8 GPa or more, and thus, it will be noted that the
insulation film has a mechanical strength satisfying the standard
required for an interlayer insulation film of semiconductor
devices.
SECOND EMBODIMENT
[0122] On the other hand, in the development of future
high-performance semiconductor devices, it is expected that the
number of the layers of the interconnection layers is increased.
Also, in relation to the prospect use the films having a large
stress therein, it is preferable that the insulation film has a
higher mechanical strength.
[0123] Thus, in order to improve the mechanical strength of the
insulation film further, it is possible to carry out the plasma
processing of the insulation film with the processing vessel 10 to
be explained next.
[0124] FIG. 8 is a diagram showing an example of the processing
vessel 10 used for carrying out the post-processing (plasma
processing) of the insulation film schematically.
[0125] Referring to FIG. 8, the processing vessel 10 includes a
chamber 11 forming a space 11a therein and a stage 13 provided in
the chamber 11 for hold a substrate to be processed 12 by way of an
electrostatic chuck.
[0126] Thereby, it should be noted that the space 11a inside the
chamber 11 is decompressed and evacuated by evacuation means such
as a vacuum pump via at least two, preferably three evacuation
ports 11D formed at a bottom part of the chamber 11 generally in
axial symmetry with respect to the substrate 12 to be processed on
the stage 13 with a constant interval so as to surround the stage
13.
[0127] For the part of the outer wall of the chamber 11
corresponding to the substrate 12 to be processed 12, there is
disposed a microwave transmission window 17 of a dielectric
material transparent to microwave such as quartz so as to face the
substrate 12 to be processed, wherein there is inserted a plasma
gas introduction ring 20 introducing a plasma gas into the
processing vessel 11 between the microwave transmission window 17
and the processing vessel 11. Thereby, the microwave window 17 and
the plasma gas introduction ring 20 constitute an outer wall of the
chamber 11.
[0128] It should be noted that the microwave transmission window 17
has a stepped part in a rim part thereof, wherein the stepped part
engages with a corresponding stepped part provided on the plasma
gas introduction ring 20. Further, there is provided a seal ring
16A for hermetically sealing the processing space 11a.
[0129] The plasma gas introduction ring 20 is supplied with a
plasma gas from a plasma gas inlet port 20A, wherein the plasma gas
thus introduced spreads through a gas groove 20B formed in
generally annular form. The plasma gas in the gas groove 20B is
then introduced into the space 11a via plural plasma gas holes 20C
that communicate with the gas groove 20B.
[0130] On the microwave transmission window 17, there is provided a
plasma generation part 30, wherein the plasma generation part 30
includes a planar antenna plate 18 of a stainless steel alloy or
aluminum alloy applied with gold plating or silver plating and
disposed close to the microwave transmission window 17, the planar
antenna plate being with plural slots 18a and 18b, a shielding case
22 of a conductor material shielding the microwave and holding the
antenna plate 18, and a retardation plate 19 consists of a low loss
dielectric material such as Al.sub.2O.sub.3, SiO.sub.2 or
Si.sub.3N.sub.4 sandwiched between the antenna plate 18 and the
shielding case 22. Further, hermetic sealing is established by a
seal ring 16B such as an O ring in the part where the plasma
generation part 30 and the microwave transmission window 17 engage
with each other.
[0131] It should be noted that the plasma generation part 30 is
mounted upon the chamber 11 via the plasma gas introduction ring
14, and a microwave of 2.45 GHz is supplied from an external
microwave resource via a coaxial waveguide 21 connected to a
central part of the plasma generation part 30.
[0132] The microwave thus supplied is radiated to the chamber 11
from the slots on the antenna plate 18 via the microwave
transmission window 17 and is introduced into the space 11a right
underneath the microwave transmission window 17. Thereby, plasma
excitation is caused in the plasma gas supplied from the plasma gas
supply ring 20 such as Ar and hydrogen. Because the plasma thus
excited has a low electron temperature, the damage to the substrate
to be processed is minimized. Further, the plasma thus excited
forms high density plasma (10.sup.11-10.sup.13/cm.sup.3).
[0133] A waveguide 21A forming an outside part of the coaxial
waveguide 21 is connected in the shielding case 22, while a central
conductor 21B is connected at the center of the antenna plate 18
via an opening formed in the retardation plate 19. Thereby, the
microwave supplied to the coaxial waveguide 21A is radiated from
the slots as it is propagated in the radial direction between the
shielding case 22 and antenna plate 18.
[0134] Further, there may be provided a cooling part on the
shielding case 22 for cooling the microwave transmission window 17,
the antenna plate 18 and the retardation plate 19.
[0135] FIG. 9 shows the antenna plate 18 in a plan view.
[0136] Referring to FIG. 9, the antenna plate 18 is provided with a
large number of mutually perpendicular slots 18a and 18b from which
the microwave radiation is achieved. The plasma generation part 30
that uses the antenna plate 18 is called a radial line slot
antenna.
[0137] With the plasma generation part 30 of such a construction,
the microwave supplied from the coaxial waveguide 21 spreads in the
radial direction as it is propagated between the shielding case 22
and the antenna plate 18, wherein the microwave experiences
compression of wavelength by the retardation plate 19.
[0138] Thus, by forming the slots 18a and the slots 18b
intersecting perpendicularly with each other in a concentric
relationship in correspondence to the wavelength of the microwave,
it becomes possible to radiate the microwave in the form of a plane
wave of circular polarization.
[0139] By using such a plasma generation part 30, it is possible to
excite high density plasma in the processing space 11a uniformly.
The high-density plasma thus formed has a low electron temperature
of 0.7-2 eV, for example, and thus, there is caused little damaging
in the substrate 12 to be processed. Further, the chance of metal
contamination caused by the sputtering of the chamber wall of the
processing vessel 11 is minimized.
[0140] The operation regarding the film formation processing of the
processing vessel 10 is controlled, by the control means 10A, which
may include a computer (CPU) and a storage medium. Thus, the
operation such as supply and discharge of gas, control of microwave
plasma, or the like, is controlled by the control means 10A.
Thereby, the control means 10A is controlled by a program stored in
the storage medium.
[0141] In the case of applying the post-processing (plasma
processing) to the insulation film formed on the substrate by using
the processing vessel 10, for example, the program stored in the
storage medium (called also recipe) controls the control means 10A
such that the processing vessel 10 applies the plasma processing to
the insulation film formed on the substrate to be processed
according to the flowchart shown in FIG. 5 similarly to the case of
the processing chamber 300 of the first embodiment, as the
post-processing.
[0142] For example, the plasma processing can be conducted by
setting the temperature of the substrate to be processed to
400.degree. C. and the pressure of the processing space 11a to 260
Pa, and by supplying the microwave electric power of 2.45 GHz
frequency with the electric power of 2000 W, together with an Ar
gas and a hydrogen gas as the second processing gas for 5 minutes
with respective flow rates of 250 sccm and 500 sccm.
[0143] As a result of the plasma processing conducted under the
foregoing condition, an insulation film having the specific
dielectric constant of 2.44 was obtained with the film thickness of
220 nm, wherein it was confirmed that the insulation film thus
formed has the longitudinal modulus of elasticity of 16.0 GPa.
Further, in the case the insulation film was formed with the
specific dielectric constant of 2.33 and the film thickness of 375
nm, it was confirmed that the longitudinal modulus of elasticity of
the insulation films is 10.7 GPa.
[0144] Thus, in any of these cases, the insulation film shows a
high elastic modulus value of 10 GPa or more, indicating that the
film has an increased hardness and increased mechanical strength as
compared with the case of the first embodiment in which film the
plasma processing is conducted by a parallel plate plasma
processing apparatus.
[0145] It should be noted that such an insulation film of large
mechanical strength and large elastic constant is suitable for the
interlayer insulation film of multilayer interconnection structure
in view of high reliability against stress such as the one applied
at the time of CMP (chemical mechanical polishing) process. Thus,
with the use of the insulation film of the present invention, it is
possible to increase the reliability of multilayer interconnection
structure.
[0146] In order to obtain such low-K insulation film of large
elastic modulus and high reliability as noted above, there exists a
range of process condition for the plasma processing used for the
post-processing of the insulation film as will be explained
below.
[0147] FIG. 10A shows the change of the longitudinal elastic
modulus of the insulation film for the case the pressure of the
processing space 11a is changed variously at the time of the plasma
processing of the insulation film, while FIG. 10B shows the change
of the specific dielectric constant of the insulation film for the
case in which the pressure of the processing space 11a at the time
of the plasma processing of the insulation film is changed.
[0148] Referring to FIG. 10A, it can be seen that there occurs some
change of the elastic modulus for the insulation film with the
change of the pressure of the processing space 11a at the time of
the plasma processing, while the elastic modulus of the insulation
film maintains the value of 10 GPa or more, and thus, the hardness
of the insulation film is maintained even when the pressure is
changed to some extent.
[0149] However, when the pressure inside the processing vessel
becomes below 10 Pa, there is caused an increase in the proportion
of ions in the active species excited in the processing vessel, and
the effect of sputtering by the ions is increased, leading to
increased degree of etching of the insulation film. Further, in the
case the pressure inside the processing vessel has exceeded 1000
Pa, there arises a concern that there may be increased degree of
film shrinkage. Therefore, it is preferable to set the pressure
inside the processing vessel at the time of the plasma processing
to be 10 Pa or more but not exceeding 1000 Pa.
[0150] Further, with reference to FIG. 10B, it can be seen that the
specific dielectric constant of the insulation film is changed in
correspondence to the change of the pressure inside the processing
vessel at the time of the plasma processing.
[0151] More specifically, it can be seen that the specific
dielectric constant decreases with increase of the pressure of the
processing space 11a in the pressure range of about 50 Pa or less,
while in the pressure region exceeding about 50 Pa, there exists a
tendency that the specific dielectric constant increases with
increase of the pressure.
[0152] From this, it is understood that there exists a desirable
pressure region for achieving a specific dielectric constant value
for the insulation film.
[0153] For example, it is preferable to set the pressure of the
processing space 11a at the time of the plasma processing to be 10
Pa or more but not exceeding 500 Pa in order to achieve the
specific dielectric constant of 3 or less, while in the case of
achieving the specific dielectric constant of 2.5 or less, it is
preferable to set the pressure of the processing space 11a at the
time of the plasma processing to 40 Pa or more but not exceeding 90
Pa.
[0154] Further, it is preferable to set the microwave electric
power applied to the plasma generation part 30 for plasma
excitation at the time of the plasma processing to be 500 W or more
but not exceeding 2000 W. When the microwave electric power is less
than 500 W, it should be noted that dissociation of the second
processing gas does not proceed satisfactorily and the effect of
the plasma processing becomes insufficient. On the other hand, when
the microwave electric power is set to be larger than 2000 W, there
can be a case that the insulation film processed with the plasma is
damaged.
[0155] FIG. 11 is a diagram showing the relationship between the
specific dielectric constant and the longitudinal elastic modulus
of the insulation film formed by the substrate processing method
according to the first embodiment and the second embodiment.
[0156] Referring to FIG. 11, an experiment PP represents the result
of the plasma processing conducted according to the first
embodiment, in other words, the case of conducting the plasma
processing of the insulation film in the processing chamber 300 of
the parallel plate plasma processing apparatus, while an experiment
MW represents the result of the plasma processing conducted
according to the second embodiment, in other words, the case of
conducting the plasma processing of the insulation film in the
processing vessel 10 of the microwave plasma processing
apparatus.
[0157] In the case of the experiment PP, the plasma processing has
been conducted under the condition in which the high frequency
electric power is set to 500-2000 W and the pressure inside the
processing vessel is set to 30-100 Pa. On the other hand, in the
case of the experiment MW, the plasma processing was conducted
under the condition in which the microwave electric power is set to
500-2000 W and the pressure inside the processing vessel is set to
50-266 Pa.
[0158] Referring to FIG. 11, it can be seen that a high elastic
modulus is attained in the case of the experiment MW that uses the
processing vessel 10 for the microwave plasma processing as
compared with the case of conducting the plasma processing by using
the parallel-plate apparatus. Thus, the insulation film formed with
the experiment MW has excellent hardness and mechanical strength
and is thought suitable for use as an interlayer insulation
film.
[0159] It is believed that the foregoing results have been obtained
as a result of the use of the plasma generation part 30 that
excites the microwave plasma of low electron temperature and high
density. For example, an insulation film of the dielectric constant
of 2.5 or less and the elastic modulus of 10 GPa or more is
achievable with the present invention.
[0160] Further, FIG. 11 shows the result of an experiment PPL, in
which the processing time of the experiment PP is increased by five
times. The point PPL indicates that it would require a long
processing time when attempt is made to form a hard insulation film
of high elastic modulus by using such a parallel plate plasma
processing apparatus.
[0161] By using the microwave plasma with the processing vessel 10
as in the case of the experiment MW, on the other hand, it is
possible to form an insulation film of high elastic modulus and
large mechanical strength with a time of about 1/5 the time needed
when using a parallel-plate plasma processing apparatus. It is
concluded that the use of microwave plasma processing is more
effective for obtaining an insulation film of the specific
dialectic constant of 2.5 or less and the elastic modulus of 8
GPa.
[0162] It should be noted that the specific dielectric constant and
the mechanical strength of the insulation film also changes when
the gap G shown in FIG. 8 representing the distance between the
microwave transmission window 17 and the substrate 12 to be
processed in the processing vessel 10.
[0163] FIG. 12 is a diagram showing the relationship between the
specific dielectric constant and the longitudinal elastic modulus
of the insulation film after the plasma processing while changing
the gap G of the processing vessel 10 variously. More specifically,
FIG. 12 shows the result for the cases in which the gap G is set to
35 mm, 55 mm and 105 mm.
[0164] Referring to FIG. 12, it can be seen that there is a
tendency that the specific dielectric constant of the insulation
film becomes low and the elastic modulus becomes large by setting
the gap G to 55 mm as compared with the case of setting the gap G
to 105 mm. Similarly, it can be seen that there is a tendency that
the specific dielectric constant of the insulation film becomes low
and the elastic modulus becomes large by setting the gap G to 35 mm
as compared with the case of setting the gap G to 55 mm.
[0165] Thus, it is preferable to narrow the gap G in order to form
an insulation film of low specific dielectric constant and
excellent mechanical strength. Thus, in order to form an insulation
film of the specific dielectric constant of 2.5 or less and the
elastic modulus of 8GPa or more, it is preferably to set the gap G
to be 55 mm or less.
[0166] On the other hand, when the gap G is excessively narrowed,
it becomes difficult to control the temperature rise of the
substrate to be processed, and there arises a concern that the
substrate to be processed may be damaged. Thus, it is preferable to
set the gap G to be 10 mm or more.
THIRD EMBODIMENT
[0167] Meanwhile, in the case the insulation film is formed by the
processing chamber 200 shown in FIG. 3, there can be a case in
which it is difficult to remove the insulation film containing Si
and C and adhered to the chamber wall 201, the showerhead 201B, the
stage 201A, and the like, inside the processing vessel 201, by way
of cleaning process.
[0168] In the case of a silicon oxide film (SiO.sub.2 film) used
conventionally, etching of the silicon oxide film is achieved
easily by ions or radicals formed by exciting a gas containing
fluorine such as a CF family gas or a NF.sub.3 gas by plasma.
[0169] In the case the insulation film contains Si and C as in the
case of an SiC film, an SiCO film or SiCO(H) film, there occurs
extreme decrease of etching rate when the ions or radicals formed
by the CF family gas or NF.sub.3 gas are used, leading to the
problem of prolonged cleaning time. Further, such prolonged
cleaning time raises the problem in that the processing vessel, in
which the cleaning is conducted, may be damaged.
[0170] For example, while it is possible to increase the etching
rate by using a gas such as an HF gas, it was inevitable that the
interior of the processing vessel undergoes a damage to some extent
with the use of HF in view of the fact that the processing vessel
is usually formed of a metal such as Al or Al alloy.
[0171] Accordingly, the present embodiment provides a cleaning
method of the processing vessel wherein the foregoing problems are
eliminated.
[0172] When conducting the cleaning method of the present
embodiment, the processing chamber 200 shown in FIG. 3 is modified
as noted below.
[0173] FIG. 13 is a diagram schematically showing the construction
of a processing apparatus 200A to which the cleaning method and
substrate processing method of the present embodiment is applied,
wherein those parts in the drawing corresponding to the parts
explained previously are designated by the same reference numerals
and the description thereof will be omitted.
[0174] Referring to the drawing, the shower head 201B is connected
with the gas line 202 used for supplying an organic silane gas
containing Si and C such as trimethyl silane (SiH(CH.sub.3).sub.3)
as the source gas of film formation of the insulation film
similarly as before, wherein, with the processing apparatus 200A of
the present embodiment, a gas line for supplying a cleaning gas is
connected to the showerhead 201B for the purpose of cleaning the
interior of the processing vessel 201. Thereby, it should be noted
that the gas line 206 is connected with a gas line 206a having a
valve 206A for supplying a cleaning gas as a third processing gas
and a gas line 206b having a valve 206B for supplying another
cleaning gas as a fourth processing gas.
[0175] The gas line 206a is connected to a gas source not
illustrated and a gas containing oxygen such as an oxygen gas is
supplied from the gas line 206a to the interior of the processing
vessel 201 via the showerhead 201B as the third processing gas for
cleaning.
[0176] Similarly, the gas line 206b is connected to a gas source
not illustrated and a gas containing fluorine such as a NF.sub.3
gas is supplied from the gas line 206b to the interior of the
processing vessel 201 via the showerhead 201B as the fourth
processing gas for cleaning. Further, the gas lines 203a and 203b
are used for supplying an inert dilution gas according to the
needs.
[0177] The substrate processing method of forming an insulation
film on the substrate Wf to be processed in the processing
apparatus 200A and further performing the cleaning process of the
processing vessel will be conducted according to the flowchart of
FIG. 14 as follows.
[0178] Referring to FIG. 14, a gate valve provided to the
processing apparatus 200A is opened in a step 600 (designated in
the drawing as S600; similar designation will be used throughout)
and the substrate to be processed is introduced into the processing
vessel 201, wherein the substrate thus introduced is placed on the
stage 201A.
[0179] Next, in a step 700, formation of the insulation film is
conducted on the substrate according to the process explained with
reference to the first embodiment.
[0180] There, an insulation film containing Si and C, such as an
SiCO(H) film, is formed on the substrate to be processed as a
result of plasma decomposition of the gas and associated
deposition.
[0181] Next, in a step 800, the substrate is taken out from the
processing vessel 201 in the step 800. By repeating the film
formation process D from the step 600 to the step 800 for plural
times, there can be formed insulation films on plural substrates in
succession.
[0182] On the other hand, in the film formation process D, there
occurs deposition of the insulation film also in the interior of
the processing vessel 201 including the shower head 201B and the
stage 201A provided therein, and thus, there arises a need of
conducting a cleaning process of the processing vessel 201.
[0183] Thus, in the substrate processing of the present embodiment,
a cleaning process C is conducted in the step 900 for cleaning the
interior of the processing vessel 201.
[0184] Thereby, the foregoing cleaning process may be conducted
each time a substrate is processed for forming the insulation film
thereon, or alternatively after processing of every 25 substrates.
In the latter case, the insulation films corresponding to the 25
substrates are cleaned at the same time.
[0185] Conventionally, there has been a case in which the cleaning
process becomes difficult when a cleaning process used
conventionally for film formation of a silicon oxide film is
applied to the case of film formation of the insulation film
containing Si and C because of small etching rate.
[0186] Thus, with the present embodiment, a plasma processing is
applied with the third processing gas containing oxygen for
facilitating oxidation of the insulation film and then conducts
plasma processing with the fourth processing gas containing
fluorine for removing the highly oxidized insulation film by
etching.
[0187] With this, there is caused increase of the etching rate for
the insulation film containing Si and C, and it becomes possible to
reduce the time needed for the cleaning process. With this, it
becomes possible to conduct the cleaning process without damaging
the processing vessel.
[0188] Next, the details of the step 900 will be explained with
reference to FIG. 15 showing the cleaning process of the present
embodiment.
[0189] FIG. 15 is a flowchart showing the details of the cleaning
method according to the present embodiment.
[0190] Referring to FIG. 15, the cleaning process is started with a
step 910, and a step 920 is conducted thereafter, wherein the third
processing gas such as an oxygen gas is introduced into the
processing vessel 201 via the showerhead 201 by opening the valve
206A with a flow rate of 200 sccm. The pressure inside the
processing vessel 201 is set to 60 Pa.
[0191] Next, in a step 930, a high frequency power of 1000 W is
applied to the shower head 201B from the high frequency source 204,
and with this, high frequency plasma is excited in the chamber 201.
Thereby, oxidation is promoted for the insulation film containing
Si and C and deposited on the interior of the processing vessel 201
including the showerhead 201B and the stage 201A by using the
oxygen radicals and the oxygen ions in the oxygen plasma.
[0192] In this process, the temperature of the processing vessel
201 is maintained at 50-200.degree. C., preferably 100-150.degree.
C. by a wall heater provided to the processing vessel 201 not shown
in FIG. 13 for the purpose of increasing the etching rate of the
insulation film. During this process, it is preferable to set the
temperature of the stage to 100-450.degree. C. In the illustrated
example, the temperature is set to 350.degree. C.
[0193] Next, in a step 940, the valve 206A is closed and the
feeding of the high frequency power is terminated. With this, the
plasma is turned off.
[0194] Next, in a step 950, the valve 206B is opened and the fourth
processing gas containing fluorine such as the NF.sub.3 gas is
introduced into the procession vessel 201 via the shower head 201B
with a flow rate of 150 sccm. Thereby, the pressure inside the
processing vessel 201 is set to 60 Pa.
[0195] Next, in the step 960, a high frequency power of 1500 W is
fed from the high frequency power source 204 to the showerhead 201B
and high frequency plasma is formed inside the processing vessel
201. With this, the insulation film deposited inside the processing
vessel 201 including the showerhead 201B and the stage 201A is
etched away by the fluorine radicals and fluorine ions in the
NF.sub.3 plasma. Thereby, it should be noted that, because the
oxidation of the insulation film containing Si and C is promoted in
the previous step 930, the insulation film is easily etched away by
the fluorine radicals and fluorine ions in the form of
SiF.sub.x.
[0196] In this process, the temperature of the processing vessel
201 is maintained to 50-200.degree. C., preferably 100-150.degree.
C. by the wall heater provided to the processing vessel 201 but not
illustrated in FIG. 13 for the purpose of increasing the etching
rate of the insulation film. During this process, it is preferable
to set the temperature of the stage to 100-450.degree. C. In the
illustrated example, the temperature is set to 350.degree. C.
[0197] Next, in a step 970, the valve 206B is closed and the
feeding of the high frequency power is terminated. Thereby the
plasma is turned off, and the cleaning process is completed in a
step 980.
[0198] Thus, with the present embodiment, the oxygen processing
step C1 corresponding to the steps 920-940 of FIG. 15 is conducted
for promoting the oxidation of the insulation film containing Si
and C by using the plasma of the third processing gas containing
oxygen such as the oxygen plasma. Thereby, there is a possibility
that a part of C is removed in the form of CO.sub.2.
[0199] Thus, in the steps 950-970 of FIG. 15, the etching is
applied to the insulation film in which the oxidation process has
been promoted and a part of C (carbon) is removed, by using the
plasma of the fourth processing gas containing fluorine such as the
NF.sub.3 plasma, and thus, the etching rate is improved
substantially as compared with the conventional art process.
[0200] A comparison was made for the cleaning time between the case
of using the method of the present embodiment shown in FIGS. 14 and
15 and the case of using a conventional method, and it was
confirmed that the cleaning time is reduced with the present
embodiment.
[0201] More specifically, the present embodiment was compared for
the cleaning time with the conventional case in which the oxygen
processing step C1 is omitted. In both of these cases, the
insulation film containing Si and C was formed in the film
formation step D of FIG. 14 by repeating the step of forming the
insulation film with the thickness of 50 nm for 25 times.
[0202] With this experiment, it was confirmed that the insulation
film is not removed completely with the conventional process even
when the processing of the step 960 is conducted for the duration
45 minutes, and thus, it was confirmed that a process time of 45
minutes or more is needed for achieving the desired cleaning with
the conventional process.
[0203] In the case of the present embodiment, on the other hand, it
was confirmed that the insulation film containing Si and C and
deposited inside the processing vessel 201 such as the inner
surface of the vessel 201, the stage 201A and the showerhead 201B,
can be removed completely by conducting the step 930 for ten
minutes, the step 950 for 15 minutes, and thus, the plasma process
in total of 25 minutes.
[0204] Because of the reduced cleaning time, the duration in which
the processing vessel is exposed to the plasma is reduced, and
thus, the damage caused in the processing vessel 201 by the plasma
can be reduced. Thereby, metal contamination or formation of
particles associated with the plasma damage is successfully
suppressed. Further, because of the reduced plasma damage, the
maintenance cycle of the apparatus can be increased and the cost of
the expensive cleaning gas is also reduced as a result of decrease
of the cleaning time. Thereby, the running cost of the apparatus
can be reduced.
[0205] Further, with the present embodiment, which uses the
so-called parallel-plate plasma processing construction in which
the plasma is excited between the showerhead 201B and the stage
201A, it becomes possible to reduce the consumption of the cleaning
gas used for the cleaning process as compared with the case of the
so-called remote plasma construction in which the plasma is
generated by a separate plasma generator and the radicals formed
with the plasma are introduced into the processing vessel for the
cleaning process. Thereby, the running cost of the apparatus is
reduced.
[0206] Further, the present embodiment uses the same plasma source
for the film formation and the cleaning, and thus, the construction
of the substrate processing apparatus is simplified. Thereby, the
cost of the substrate processing apparatus can be reduced.
[0207] Further, as compared with a high-density plasma source such
as an ICP (induction-coupled plasma) source, the parallel-plate
plasma apparatus has an advantageous feature of simple construction
and low apparatus cost.
[0208] While the present embodiment has been explained for the case
of using oxygen for the third processing gas, it is also possible
to dilute the third processing gas by an inert gas such as Ar, He,
or the like, according to the needs. Further, it is possible to use
a compound gas containing O such as N.sub.2O in place of the oxygen
gas. Further, the same effect as the present embodiment is attained
also by using an ozone gas.
[0209] With regard to the fourth processing gas, it is possible to
use other etching gas containing F in addition to NF.sub.3, such as
a fluorocarbon gas including a CF.sub.4 gas, a C.sub.2F.sub.6 gas,
a C.sub.5F.sub.8 gas, and the like. Further, a similar effect is
attained also by using an SF.sub.6 gas.
[0210] Further, while the present embodiment has been explained for
the case of using trimethyl silane for the organic silane gas at
the time of the film formation process as the film formation gas,
while it is also possible to use other organic silane gas for the
film formation of the insulation film. For example, it is possible
to use a dimethyl dimethoxy silane gas (DMDMOS) for this
purpose.
[0211] Further, it is possible to use the silane (SiH.sub.4) gas
admixed with another gas for the source gas of the film formation
processing. For example, it is possible to form an SiC film, an
SiCO film, an SiCO(H) film, and the like, by using a silane gas
admixed with an oxygen gas and a hydrocarbon gas such as a methane
gas, an ethane gas, and the like, as the source gas of the film
formation processing. Similarly, it is possible to form an SiC
film, an SiCO film, an SiCO(H) film, or the like, by adding
methanol, ethanol, and the like, to the silane gas. Further, it is
also possible to form a film containing nitrogen such as a SiCN
film.
[0212] It should be noted that the insulation film containing Si
and C formed with the present embodiment can be used in the
fabrication process of a semiconductor device having a multilayer
interconnection structure as a low-K hard mask film at the time of
etching an interlayer insulation film. It should be noted that the
low-K film of the present invention does not cause the problem of
increase of the parasitic capacitance between the interconnection
layers and can be used successfully for the hard mask.
[0213] Further, the insulation film containing Si and C of the
present invention can be used for the low-K interlayer insulation
film of the semiconductor device. With the use of such a low-K
insulation film of the present invention, the parasitic capacitance
between the interconnection patterns can be reduced
effectively.
[0214] When using the insulation film of the present invention, it
is preferable to increase the amount of oxygen or hydrogen added to
the film as compared with the case of using the insulation film as
a hard mask, such that the film has a composition of SiCO or
SiCO(H). Thereby, the specific dielectric constant can be reduced
further.
[0215] Thus, the cleaning technology of the present embodiment is
effective and useful for cleaning the processing vessel at the time
of formation of the insulation film of low dielectric constant
suitable for the low-K hard mask film or low-K interlayer
insulation film used for the multilayer interconnection structure
of high-speed semiconductor devices.
FOURTH EMBODIMENT
[0216] The foregoing third embodiment of the present invention can
be modified as noted below, with substantially the same effect.
[0217] FIG. 16 is a flowchart showing a cleaning process according
to a fourth embodiment of the present invention, wherein the
cleaning process of FIG. 16 is a modification of the cleaning
process of FIG. 15. In the drawing, those parts corresponding to
the parts explained previously are designated by the same reference
numerals and the description thereof will be omitted.
[0218] In the present embodiment, the process is controlled to
return to the step 920 after the completion of the step 970, and
thus, the steps from the step 920 to the step 970 corresponding to
the oxygen processing step C1 and the processing step C2 for
processing by the fluorine-containing gas are repeated. After
repetition of the process steps from the step 920 to the step 970
for a predetermined time, the process is terminated at the step
980.
[0219] Thus, with the present embodiment, oxidation of the
insulation film or removal of C from the insulation film is
conducted efficiently in addition to the effect of the third
embodiment explained previously, and it becomes possible to
increase the etching rate of the insulation film further.
[0220] For example, in the case the insulation film to be etched
has a large thickness, the oxidation processing may not penetrate
to the interior of the insulation film sufficiently with the
process C1 from the step 920 to the step 940 and the effect of
removing the carbon inside the insulation film may not be
sufficient. In such a case, there is a concern that the etching
rate of the insulation film may decrease in the steps from the step
950 to the step 970 corresponding to the process C2 with the
progress of etching of the invention film.
[0221] With the present embodiment, on the other hand, the oxygen
processing step C1 and the processing step C2 conducted by the
fluorine-containing gas are repeatedly implemented, and thus, there
is conducted the oxygen processing step C1 after the etching of the
insulate film. Thereby, the oxidation of the insulation film and
the removal of C from the insulation film are ensured even when the
etching process has been progressed with the insulation film. Thus,
decrease of the etching rate can be prevented even when the etching
of the insulation film has proceeded, and high etching rate is
maintained until all the insulation film is etched out.
[0222] Further, because the present embodiment is particularly
effective in the case the insulation film to be etched has a large
thickness, the present embodiment is particularly effective when
conducting the cleaning for the insulation film corresponding to
plural substrates such as 25 substrates after processing the film
formation process D of FIG. 14 for plural times corresponding to
the 25 substrates.
[0223] In view of the transportation time of the substrates to be
processed, the cleaning processing can be conducted more
efficiently by processing plural substrates at once after film
formation on such plural substrates than processing the substrates
one by one each time film formation is made on a substrate. Thus,
the present embodiment is a technology suitable for improving the
efficiency of substrate processing.
FIFTH EMBODIMENT
[0224] Next, a fifth embodiment of the present invention will be
described with reference to FIG. 17, wherein the present embodiment
is another modification of the cleaning process according to the
third embodiment of the present invention. In FIG. 17, those parts
corresponding to the parts explained previously are designated by
the same reference numerals and the description thereof will be
omitted.
[0225] Referring to FIG. 17, there is conducted a step 950A after
the step 930 with the present embodiment to open the valve 206B and
introduce the fourth processing gas such as the NF.sub.3 gas into
the processing vessel 201 via the shower head 201B with a flow rate
of 150 sccm.
[0226] In the step 970, the valves 206A and 206B are closed and the
feeding of the high frequency power is terminated. Further, the
processing is terminated with the step 980.
[0227] In the present invention, it should be noted that the fourth
processing gas is introduced in the state that there is formed
plasma of the third processing gas. Thus, in addition to the
foregoing effect of the third embodiment, the present embodiment
can provide the advantageous effect of simple control process for
the cleaning processing. Thereby the time needed for the cleaning
processing is reduced.
[0228] In the present embodiment, it should be noted that the
etching of the insulation film by fluorine proceeds simultaneously
to the oxidation of the insulation film and removal of C. Thereby,
it is possible to reduce the amount of the third processing gas
introduced in the step 950 according to the needs. Alternatively,
it is possible to interrupt the introduction of the third
processing gas in the step 950A,
SIXTH EMBODIMENT
[0229] Next, a sixth embodiment of the present invention will be
described with reference to FIG. 18, wherein the present embodiment
is another modification of the cleaning process according to the
third embodiment of the present invention. In FIG. 18, those parts
corresponding to the parts explained previously are designated by
the same reference numerals and the description thereof will be
omitted.
[0230] Referring to FIG. 18, the present embodiment opens the valve
206A and the valve 206B in a step 920A conducted after the step 910
and the third processing gas and the fourth processing gas are
introduced into the processing vessel 201 via the shower head
201B.
[0231] Thus, with the present embodiment, oxidation of the
insulation film and removal of C from the insulation film proceed
simultaneously to the etching process conducted by fluorine.
Thereby, with the present embodiment, in which the third and fourth
processing gases are introduced simultaneously, an advantageous
feature that the control of the cleaning processing is simplified
is attained, in addition to the advantageous effect explained with
reference to the third embodiment, and the time needed for the
cleaning process is reduced. Further, because the third processing
gas and the fourth processing gas are introduced simultaneously, it
is possible with the present embodiment to reduce the number of the
gas lines and hence the cost of the substrate processing
apparatus.
[0232] It should be noted that the etching rate of the insulation
film containing Si and C changes depending on the composition
thereof. For example, the contribution of oxidation of the
insulation film or removal of C therefrom on the etching rate may
increase depending on the composition of the insulation film.
Thereby, there can be a case in which the etching rate increases in
the event the oxidation processing step C1 is conducted in advance
of the fluorine processing step C2. In this case, the cleaning time
may decrease in the case of the third through fifth embodiments as
compared with the present embodiment.
[0233] Thus, in view of the foregoing effect, it is preferable to
choose most preferable process from the process of the third
embodiment to the process of the sixth embodiment, according to the
needs.
[0234] According to the present invention, it becomes possible to
decrease the dielectric constant of the insulation film formed by
an organic silane gas and achieve the improvement of mechanical
strength at the same time.
[0235] Further, the present invention is not limited to the
embodiments described heretofore, but various variations and
modifications may be made without departing from the scope of the
invention.
* * * * *