U.S. patent application number 10/367762 was filed with the patent office on 2003-08-14 for plasma thin-film deposition method.
This patent application is currently assigned to TOKYO ELECTRON LIMITED. Invention is credited to Nakase, Risa.
Application Number | 20030152714 10/367762 |
Document ID | / |
Family ID | 26389222 |
Filed Date | 2003-08-14 |
United States Patent
Application |
20030152714 |
Kind Code |
A1 |
Nakase, Risa |
August 14, 2003 |
Plasma thin-film deposition method
Abstract
In a case where a CF film is used as an interlayer dielectric
film for a semiconductor device, when a wiring of W (tungsten) is
formed, the CF film is heated to a temperature of, e.g., about 400
to 450.degree. C. At this time, F gases are desorbed from the CF
film, so that there are various disadvantages due to the corrosion
of the wiring and the decrease of film thickness. As thin-film
deposition gases, cyclic C.sub.5F.sub.8 gas and a hydrocarbon gas,
e.g., C.sub.2H.sub.4 gas, are used. These gases are activated as
plasma under a pressure of, e.g., 0.1 Torr, to deposit a CF film on
a semiconductor wafer at a process temperature of 400.degree. C.
using active species thereof. Alternatively, cyclic C.sub.6F.sub.6
gas is used as a thin-film deposition gas, and activated as plasma
under a pressure of, e.g., 0.06 Pa, to deposit a CF film on a
semiconductor wafer at a process temperature of 400.degree. C.
using active species thereof.
Inventors: |
Nakase, Risa;
(Sagamihara-Shi, JP) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT & DUNNER
LLP
1300 I STREET, NW
WASHINGTON
DC
20005
US
|
Assignee: |
TOKYO ELECTRON LIMITED
Tokyo
JP
|
Family ID: |
26389222 |
Appl. No.: |
10/367762 |
Filed: |
February 19, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10367762 |
Feb 19, 2003 |
|
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|
09578726 |
May 26, 2000 |
|
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6544901 |
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09578726 |
May 26, 2000 |
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PCT/JP98/05219 |
Nov 19, 1998 |
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Current U.S.
Class: |
427/457 ;
257/E21.264; 257/E21.266; 257/E21.576 |
Current CPC
Class: |
C23C 16/30 20130101;
H01L 21/0212 20130101; H01L 21/314 20130101; H01L 21/3127 20130101;
C23C 16/26 20130101; H01L 21/02274 20130101; H01L 21/76801
20130101 |
Class at
Publication: |
427/457 |
International
Class: |
G21H 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 27, 1997 |
JP |
343998/1997 |
Feb 13, 1998 |
JP |
048882/1998 |
Claims
1. A plasma thin-film deposition method comprising the steps of:
activating a thin-film deposition gas containing cyclic
C.sub.5F.sub.8 gas to form a plasma; and depositing an insulator
film of a fluorine containing carbon film on a substrate to be
treated, with said plasma.
2. A plasma thin-film deposition method as set forth in claim 1,
wherein said thin-film deposition gas contains cyclic
C.sub.5F.sub.8 gas and at lease one of a hydrocarbon gas and
hydrogen.
3. A plasma thin-film deposition method as set forth in claim 1,
wherein said insulator film is deposited under a process pressure
of 5.5 Pa or lower.
4. A plasma thin-film deposition method as set forth in claim 1,
wherein the temperature of said substrate to be treated is
360.degree. C. or higher.
5. A plasma thin-film deposition method comprising the steps of:
activating a thin-film deposition gas containing linear
C.sub.5F.sub.8 gas to form a plasma; and depositing an insulator
film of a fluorine containing carbon film on a substrate to be
treated, with said plasma.
6. A plasma thin-film deposition method as set forth in claim 5,
wherein said thin-film deposition gas contains linear
C.sub.5F.sub.8 gas and at lease one of a hydrocarbon gas and
hydrogen.
7. A plasma thin-film deposition method as set forth in claim 5,
wherein said insulator film is deposited under a process pressure
of 0.3 Pa or lower.
8. A plasma thin-film deposition method as set forth in claim 5,
wherein the temperature of said substrate to be treated is
360.degree. C. or higher.
9. A plasma thin-film deposition method comprising the steps of:
activating a thin-film deposition gas containing a gas of a benzene
ring containing compound to form a plasma; and depositing an
insulator film of a fluorine containing carbon film on a substrate
to be treated, with said plasma.
10. A plasma thin-film deposition method as set forth in claim 9,
wherein said benzene ring containing compound is a compound of C
and F.
11. A plasma thin-film deposition method as set forth in claim 10,
wherein said compound of C and F is C.sub.6F.sub.6.
12. A plasma thin-film deposition method as set forth in claim 10,
wherein said compound of C and F is C.sub.7F.sub.8.
13. A plasma thin-film deposition method as set forth in claim 9,
wherein said benzene ring containing compound is a compound of C, F
and H.
14. A plasma thin-film deposition method as set forth in claim 13,
wherein said compound of C, F and H is C.sub.7H.sub.5F.sub.3.
Description
TECHNICAL FIELD
[0001] The present invention relates to a method for depositing a
fluorine containing carbon film, which can be used as, e.g., an
interlayer dielectric film (an interlayer dielectric film) of a
semiconductor device, by a plasma treatment.
BACKGROUND ART
[0002] In order to achieve the high integration of a semiconductor
device, it has been developed to provide devices, such as the scale
down of a pattern and the multilayering of a circuit. As one of
such devices, there is a technique for multilayering wirings. In
order to provide a multi-layer metallization structure, a number n
wiring layer and a number (n+1) wiring layer are connected to each
other by means of a conductive layer, and a thin-film called an
interlayer dielectric film as an interlayer dielectric film is
formed in a region other than the conductive layer.
[0003] A typical interlayer dielectric film is an SiO.sub.2 film.
In recent years, in order to more accelerate the operation of a
device, it has been required to reduce the relative dielectric
constant of the interlayer dielectric film, and the material of the
interlayer dielectric film has been studied. That is, the relative
dielectric constant of an SiO.sub.2 film is about 4, and it has
been diligently studied to dig up materials having a smaller
relative dielectric constant than that of the SiO.sub.2 film. As
one of such materials, it has been studied to put an SiOF film
having a relative dielectric constant of 3.5 to practical use. The
inventor has taken notice of a fluorine containing carbon film
(which will be hereinafter referred to as a "CF film") having a
still smaller relative dielectric constant.
[0004] FIG. 19 shows a part of a circuit part formed on a wafer,
wherein reference numbers 11 and 12 denote CF films, 13 and 14
denoting conductive layers of tungsten (W), 15 denoting a
conductive layer of aluminum (Al), 16 denoting an SiO.sub.2 film,
into which P and B have been doped, and 17 denoting an n-type
semiconductor region. The W layer 13 is formed at a process
temperature of 400 to 450.degree. C. At this time, the CF films 11
and 12 are heated to the process temperature. However, if the CF
films are heated to such a high temperature, a part of C--F bonds
are cut, so that F (fluorine) gases are mainly desorbed. The F
gasses include F, CF, CF.sub.2 gases and so forth.
[0005] If the F gases are thus desorbed, there are the following
problems.
[0006] (a) The metal wirings of aluminum, tungsten and so forth are
corroded.
[0007] (b) Although the insulator film also has the function of
pressing the aluminum wiring to prevent the swell of aluminum, the
pressing force of the insulator film on the aluminum wiring is
decreased by the degassing. As a result, the aluminum wiring
swells, so that an electrical defect called electromigration is
easily caused.
[0008] (c) The insulator film cracks, so that the insulation
performance between the wirings gets worse. When the extent of the
crack increases, it is not possible to form any wiring layers at
the next stage.
[0009] (d) If the amount of desorbed F increases, the relative
dielectric constant increases.
DISCLOSURE OF THE INVENTION
[0010] It is therefore an object of the present invention to
eliminate the aforementioned problems and to provide a method
capable of depositing an insulator film of a CF film, which has
strong bonds and which is difficult to be decomposed, e.g., an
interlayer dielectric film of a semiconductor device.
[0011] According to one aspect of the present invention, according
to a first aspect of the present invention, a plasma thin-film
deposition method comprises the steps of: activating a thin-film
deposition gas containing cyclic C.sub.5F.sub.8 gas to form a
plasma; and depositing an insulator film of a fluorine containing
carbon film on a substrate to be treated, with the plasma.
[0012] The thin-film deposition gas may contain cyclic
C.sub.5F.sub.8 gas and at lease one of a hydrocarbon gas and
hydrogen. The insulator film may be deposited under a process
pressure of 5.5 Pa or lower. The temperature of the substrate to be
treated may be 360.degree. C. or higher.
[0013] According to a second aspect of the present invention, a
plasma thin-film deposition method comprises the steps of:
activating a thin-film deposition gas containing linear
C.sub.5F.sub.8 gas to form a plasma; and depositing an insulator
film of a fluorine containing carbon film on a substrate to be
treated, with the plasma.
[0014] The thin-film deposition gas may contain linear
C.sub.5F.sub.8 gas and at lease one of a hydrocarbon gas and
hydrogen. The insulator film may be deposited under a process
pressure of 0.3 Pa or lower. The temperature of the substrate to be
treated may be 360.degree. C. or higher.
[0015] According to a third aspect of the present invention, a
plasma thin-film deposition method comprises the steps of:
activating a thin-film deposition gas containing a gas of a benzene
ring containing compound to form a plasma; and depositing an
insulator film of a fluorine containing carbon film on a substrate
to be treated, with the plasma.
[0016] The benzene ring containing compound may be a compound of C
and F. The compound of C and F may be C.sub.6F.sub.6. The compound
of C and F may also be C.sub.7F.sub.8. Alternatively, the benzene
ring containing compound may be a compound of C, F and H. The
compound of C, F and H may be C.sub.7H.sub.5F.sub.3.
[0017] According to the first through third aspects of the present
invention, it is possible to produce a CF film which has high
thermostability and a small amount of desorbed F gas. Therefore, if
this CF film is used as, e.g., an interlayer dielectric film of a
semiconductor device, it is possible to prevent the corrosion of a
metal wiring, the swell of an aluminum wiring and the crack of the
film. Since CF films have been widely noticed as insulator films
having a small relative dielectric constant and since the scale
down and high integration of semiconductor devices have been
required, the present invention is effective in the practical use
of CF films as insulator films.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a longitudinal section of an example of a plasma
treatment system for carrying out a method according to the present
invention;
[0019] FIG. 2 is a schematic diagram for explaining the
decomposition and recombination of a thin-film deposition gas for
use in the first preferred embodiment of the present invention;
[0020] FIG. 3 is a characteristic diagram showing the results of a
mass spectrometry when cyclic C.sub.5F.sub.8 gas is decomposed;
[0021] FIG. 4 is a schematic diagram for explaining the
decomposition and recombination of C.sub.4F.sub.8 gas compared with
the thin-film deposition gas for use in the first preferred
embodiment of the present invention;
[0022] FIG. 5 is a schematic sectional view of a measuring device
for examining the variation in weight of a thin-film;
[0023] FIG. 6 is a characteristic diagram showing the relationship
between the variations in weight of a CF film, which is deposited
using cyclic C.sub.5F.sub.8 gas and C.sub.2H.sub.4 gas, and process
temperatures;
[0024] FIG. 7 is a characteristic diagram showing the relationship
between the variations in weight of a CF film, which is deposited
using cyclic C.sub.5F.sub.8 gas and C.sub.2H.sub.4 gas, and the
flow ratios of thin-film deposition gases;
[0025] FIG. 8 is a characteristic diagram showing the relationship
between the variations in weight of a CF film, which is deposited
using cyclic C.sub.5F.sub.8 gas and C.sub.2H.sub.4 gas, and process
pressures;
[0026] FIG. 9 is a characteristic diagram showing the relationship
between the variations in weight of a CF film, which is deposited
using cyclic C.sub.5F.sub.8 gas and C.sub.2H.sub.4 gas, and process
temperatures;
[0027] FIG. 10 is a characteristic diagram showing the relationship
between the variations in weight of a CF film, which is deposited
using cyclic C.sub.5F.sub.8 gas and C.sub.2H.sub.4 gas, and the
flow ratios of thin-film deposition gases;
[0028] FIG. 11 is a characteristic diagram showing the relationship
between the variations in weight of a CF film, which is deposited
using cyclic C.sub.5F.sub.8 gas and C.sub.2H.sub.4 gas, and process
pressures;
[0029] FIG. 12 is a characteristic diagram showing the relationship
between the variations in weight of a CF film, which is deposited
using linear C.sub.5F.sub.8 gas and C.sub.2H.sub.4 gas, and process
temperatures;
[0030] FIG. 13 is a characteristic diagram showing the relationship
between the variations in weight of a CF film, which is deposited
using linear C.sub.5F.sub.8 gas and C.sub.2H.sub.4 gas, and the
flow ratios of thin-film deposition gases;
[0031] FIG. 14 is a characteristic diagram showing the relationship
between the variations in weight of a CF film, which is deposited
using linear C.sub.5F.sub.8 gas and C.sub.2H.sub.4 gas, and process
pressures;
[0032] FIG. 15 is a characteristic diagram showing the results of a
mass spectrometry when linear C.sub.5F.sub.8 gas is decomposed;
[0033] FIG. 16 is a schematic diagram showing the variations in
weight of CF films in Examples and Comparative Examples;
[0034] FIG. 17 is a characteristic diagram showing the results of a
mass spectrometry when C.sub.4F.sub.8 gas is decomposed;
[0035] FIG. 18 is a characteristic diagram showing the results of a
mass spectrometry for CF films at a high temperature;
[0036] FIG. 19 is a structural drawing showing an example of the
structure of a semiconductor device;
[0037] FIG. 20 is a schematic diagram for explaining the
decomposition and recombination of a thin-film deposition gas for
use in the second preferred embodiment of the present
invention;
[0038] FIG. 21 is a schematic diagram showing molecular formulae of
examples of thin-film deposition gases;
[0039] FIG. 22 is a schematic diagram showing molecular formulae of
examples of thin-film deposition gases;
[0040] FIG. 23 is a schematic diagram showing the variations in
weight in Examples and Comparative Examples;
[0041] FIG. 24 is a characteristic diagram showing the results of a
mass spectrometry for CF films at a high temperature in
Example;
[0042] FIG. 25 is a characteristic diagram showing the results of a
mass spectrometry for CF films at a high temperature in Comparative
Example;
[0043] FIG. 26 is a characteristic diagram showing the results of a
mass spectrometry when hexafluorobenzene is decomposed;
[0044] FIG. 27 is a characteristic diagram showing the results of a
mass spectrometry when octafluorotoluene is decomposed; and
[0045] FIG. 28 is a characteristic diagram showing the results of a
mass spectrometry when 1,4-bistrifluoromethylbenzene is
decomposed.
BEST MODE FOR CARRYING OUT THE INVENTION
[0046] FIG. 1 shows an example of a plasma treatment system for use
in the preferred embodiments of the present invention. This system
has a vacuum vessel 2 of, e.g., aluminum. The vacuum vessel 2
comprises a first cylindrical vacuum chamber 21, which is arranged
in an upper portion for producing a plasma, and a second
cylindrical vacuum chamber 22, which is communicated with and
connected to the lower portion of the first vacuum chamber 21 and
which has a greater diameter than that of the first vacuum chamber
21. Furthermore, the vacuum vessel 2 is grounded to have a zero
potential.
[0047] The upper end of the vacuum vessel 2 is open. A transmission
window 23 of a microwave permeable material, e.g., quartz, is
airtightly provided in the open upper end of the vacuum vessel 2 so
as to hold vacuum in the vacuum vessel 2. Outside of the
transmission window 23, there is provided a waveguide 25 connected
to a high-frequency power supply part 24 for producing a microwave
of, e.g., 2.45 GHz. The microwave produced by the high-frequency
power supply part 24 is guided by the waveguide 25 in, e.g., a TE
mode, or the microwave guided in the TE mode is converted by the
waveguide 25 into a TM mode, to be introduced from the transmission
window 23 into the first vacuum chamber 21.
[0048] In the side wall defining the first vacuum chamber 21, gas
nozzles 31 are arranged at regular intervals along, e.g., the
periphery thereof. The gas nozzles 31 are connected to a gas source
(not shown), e.g., an Ar gas source, so that Ar gas can be
uniformly supplied to the upper portion in the first vacuum chamber
21.
[0049] In the second vacuum chamber 22, a wafer mounting table 4 is
provided so as to face the first vacuum chamber 21. The mounting
table 4 has an electrostatic chuck 41 on the surface thereof. The
electrode of the electrostatic chuck 41 is connected to a dc power
supply (not shown) for absorbing a wafer and to a high-frequency
power supply part 42 for applying a bias voltage for implanting
ions into the wafer.
[0050] On the other hand, in the upper portion of the second vacuum
chamber 22, i.e., in a portion of the second vacuum chamber 22
communicated with the first vacuum chamber 21, a ring-shaped
thin-film deposition gas supply part 51 is provided. For example,
two kinds of thin-film deposition gases are supplied from gas
supply pipes 52 and 53 to the thin-film deposition gas supply part
51, so that the mixed gas thereof is supplied to the vacuum vessel
2 via gas holes 54 formed in the inner peripheral surface of the
thin-film deposition gas supply part 51.
[0051] In the vicinity of the outer periphery of the side wall
defining the first vacuum chamber 21, a magnetic field forming
means, e.g., a ring-shaped main electromagnetic coil 26, is
arranged. Below the second vacuum chamber 22, a ring-shaped
auxiliary electromagnetic coil 27 is arranged. To the bottom of the
second vacuum chamber 22, exhaust pipes 28 are connected at, e.g.,
two positions which are symmetrical with respect to the central
axis of the vacuum chamber 22.
[0052] The first preferred embodiment of the present invention will
be described below.
[0053] A method for depositing an interlayer dielectric film of a
CF film on a wafer W, which serves as a substrate to be treated,
using the system shown in FIG. 1 will be described. First, a gate
valve (not shown) provided in the side wall of the vacuum vessel 2
is open, and the wafer W, on which a wiring of, e.g., aluminum, has
been formed, is introduced from a load-lock chamber (not shown) by
means of a transport arm (not shown) to be mounted on the mounting
table 4 to be electrostatically absorbed by means of the
electrostatic chuck 41.
[0054] Subsequently, after the gate valve is closed to seal the
interior of the vacuum vessel 2, the internal atmosphere is
exhausted by the exhaust pipes 28, and the interior of the vacuum
vessel 2 is evacuated to a predetermined degree of vacuum. Then, a
plasma producing gas, e.g., Ar gas, is introduced from the plasma
gas nozzles 31 into the first vacuum chamber 21 at a predetermined
flow rate, and a thin-film deposition gas is introduced from the
thin-film deposition gas supply part 5 into the second vacuum
chamber 22 at a predetermined flow rate.
[0055] This preferred embodiment is characterized by the thin-film
deposition gas. As shown on the left side of FIG. 2(a), cyclic
C.sub.5F.sub.8 gas is used as the thin-film deposition gas. As the
thin-film deposition gas, a hydrocarbon gas, e.g., C.sub.2H.sub.4
gas is also used. The C.sub.5F.sub.8 and C.sub.2H.sub.4 gasses are
supplied to the vacuum vessel 2 via the thin-film deposition gas
supply part 5 from the gas supply pipes 52 and 53, respectively.
Then, the interior of the vacuum vessel 2 is held under a
predetermined process pressure, and a bias voltage of 13. 56 MHz
and 1500 W is applied to the mounting table 4 by means of the
high-frequency power supply part 42. In addition, the surface
temperature of the mounting table 4 is set to be about 400.degree.
C.
[0056] A high-frequency wave (a microwave) of 2.45 GHz from the
high-frequency power supply part 24 passes through the waveguide 25
to reach the ceiling of the vacuum vessel 2, and passes through the
transmission window 23 to be introduced into the first vacuum
chamber 21. On the other hand, a magnetic field extending from the
upper portion of the first vacuum chamber 21 to the lower portion
of the second vacuum chamber 22 is formed in the vacuum vessel 2 by
the electromagnetic coils 26 and 27. The intensity of the magnetic
field is, e.g., 875 gausses in the vicinity of the lower portion of
the first vacuum chamber 21. The electron cyclotron resonance is
produced by the interaction between the magnetic field and the
microwave. By this resonance, Ar gas is activated as plasma and
enriched. The plasma flows from the first vacuum chamber 21 into
the second vacuum chamber 22 to activate C.sub.5F.sub.8 gas and
C.sub.2H.sub.4 gas, which have been supplied thereto, to form
active species to deposit a CF film on the wafer W. Furthermore,
when a device is actually produced, the CF film is etched with a
predetermined pattern, and, e.g., a W film is embedded in a groove
portion to form a W wiring.
[0057] The CF film thus deposited has a strong bond, and high
thermostability as can be seen from the results of experiment which
will be described later. That is, the amount of the desorbed F
gases is small even at a high temperature. It is considered that
the reason for this is that the decomposition products of cyclic
C.sub.5F.sub.8 are easy to form a three-dimensional structure shown
in FIG. 2, so that C--F bonds are strengthen and difficult to be
cut even if heat is applied thereto. The decomposition products of
cyclic C.sub.5F.sub.8 were vaporized under a reduced pressure of
0.002 Pa, and the vaporized decomposition products were analyzed by
means of a mass spectrometer. The obtained results are shown in
FIG. 3. It can be seen from the results that many C.sub.3F.sub.3
and C.sub.4F.sub.4, which are easy to form three-dimensional
structures, exist as decomposition products.
[0058] As a comparative example, considering a case where cyclic
C.sub.4F.sub.8 gas is used as a thin-film deposition gas, the
decomposition products of C.sub.4F.sub.8 include the most
C.sub.2F.sub.4 to easily form a straight chain structure as shown
in FIG. 4. Therefore, the thermostability of a CF film deposited
using C.sub.4F.sub.8 gas is low, as can be seen from the results of
comparative experiments which will be described later.
[0059] In view of the foregoing, C.sub.5F.sub.8 gas is essentially
used as a thin-film deposition gas according to the present
invention. As a gas added thereto, a hydrocarbon gas, such as
C.sub.2H.sub.4, CH.sub.4 or C.sub.2H.sub.6 gas, hydrogen gas or a
mixed gas of the hydrocarbon gas and hydrogen gas may be used.
EXAMPLE 1
[0060] Using a measuring device shown in FIG. 5, the variation in
weight of a thin-film at a high temperature was examined as an
index of the thermostability of the thin-film. In FIG. 5, reference
number 61 denotes a vacuum vessel, 62 denoting a heater, 63
denoting a crucible suspended from a beam of a light balance
mechanism, and 64 denoting a weight measuring part. As a measuring
method, there was adopted a method for shaving a CF film on a wafer
to put the shaven CF film in the crucible 63 to raise the
temperature in the crucible 63 to 425.degree. C. under a vacuum
atmosphere to heat the CF film for 2 hours to examine the variation
in weight in the weight measuring part 64. In the thin-film
deposition process described above in the preferred embodiment, the
temperature during the thin-film deposition was set to be any one
of seven temperatures, 300.degree. C., 325.degree. C., 350.degree.
C., 360.degree. C., 380.degree. C., 400.degree. C., 420.degree. C.
and 440.degree. C., and the variations in weight of CF films
obtained at the respective process temperatures were examined. The
results thus obtained are shown in FIG. 6.
[0061] In the above thin-film deposition process, the flow rates of
C.sub.5F.sub.8, C.sub.2H.sub.4 and Ar gases were set to be 60 sccm,
20 sccm and 150 sccm, respectively. In addition, the microwave
power (the high-frequency power supply part 24) and the bias power
(the high-frequency power supply part 42) were set to be 2000 W and
1500 W, respectively. Moreover, the process pressure was set to be
0.1 Pa. Furthermore, the variation in weight means a value of
{(A-B)/A}.times.100 assuming that the weight of the thin-film in
the crucible before heating is A and the weight of the thin-film in
the crucible after heating is B.
[0062] As can be seen from FIG. 6, the variation in weight at a
process temperature of 360.degree. C. is 2.8% which is less than
3%, and the variation in weight at a process temperature of
400.degree. C. or higher is 1.4% which is very low, so that
thermostability is high and the amount of degassing is small.
[0063] In addition, CF films were deposited at a process
temperature of 400.degree. C. at various flow ratios of
C.sub.5F.sub.8 gas to C.sub.2H.sub.4 gas when other process
conditions were the same as the above described conditions. The
variations in weight of the obtained CF films were examined. The
results thus obtained are shown in FIG. 7. Furthermore, the flow
ratio means C.sub.5F.sub.8/C.sub.2H.sub.4, and the flow rate of
C.sub.5F.sub.8 was fixed to 60 sccm. As can be seen from the
results, the variation in weight is small, 1.4%, when the flow
ratio is 3. As the flow ratio decreases, the variation in weight
decreases substantially in proportion thereto. When the flow ratio
is less than 1, it is difficult to deposit a thin-film due to film
peeling.
[0064] Moreover, CF films were deposited at a process temperature
of 400.degree. C. under various process pressures when the flow
rates of C.sub.5F.sub.8 gas and C.sub.2H.sub.4 gas were set to be
60 sccm and 20 sccm, respectively, and when other process
conditions were the same as the above described conditions. The
variations in weight of the obtained CF films were examined. The
results thus obtained are shown in FIG. 8. As can be seen from the
results, the variation in weight is small, 2% or less, when the
process pressure is lower than or equal to 5.5 Pa.
EXAMPLE 2
[0065] CF films were obtained on various process conditions using
hydrogen gas (H.sub.2 gas) in place of C.sub.2H.sub.4 gas in
Example 1. The variations in weight of the obtained CF films were
examined. First, the temperature during the thin-film deposition
was set to be any one of five temperatures, 300.degree. C.,
350.degree. C., 360.degree. C., 400.degree. C. and 420.degree. C.,
and the variations in weight of the CF films obtained at the
respective process temperatures were examined. The results thus
obtained are shown in FIG. 9.
[0066] In the above process, the flow rates of C.sub.5F.sub.8,
H.sub.2 and Ar gases were set to be 60 sccm, 40 sccm and 150 sccm,
respectively. In addition, the microwave power (the high-frequency
power supply part 24) and the bias power (the high-frequency power
supply part 42) were set to be 2000 W and 1500 W, respectively.
Moreover, the process pressure was set to be 0.2 Pa.
[0067] As can be seen from FIG. 9, the temperature dependency was
substantially the same as that in Example 1. The variation in
weight at a process temperature of 360.degree. C. is 2.8% which is
less than 3%, and the variation in weight at a process temperature
of 400.degree. C. or higher is 1.5% which is very low, so that
thermostability is high and the amount of degassing is small.
Furthermore, no thin-film was deposited due to film peeling at a
temperature of higher than 420.degree. C.
[0068] In addition, CF films were deposited at a process
temperature of 400.degree. C. at various flow ratios of
C.sub.5F.sub.8 gas to H.sub.2 gas when other process conditions
were the same as the above described conditions. The variations in
weight of the obtained CF films were examined. The results thus
obtained are shown in FIG. 10. Furthermore, the flow ratio means
C.sub.5F.sub.8/H.sub.2, and the flow rate of C.sub.5F.sub.8 was
fixed to 60 sccm. When the flow rate was less than 0.8, no
thin-film was deposited. On the other hand, even if the flow rate
exceeded 2, no thin-film was deposited. In this range, the
variation in weight was small, 2% or less.
[0069] Moreover, CF films were deposited at a process temperature
of 400.degree. C. under various process pressures when the flow
rates of C.sub.5F.sub.8 gas and H.sub.2 gas were set to be 60 sccm
and 40 sccm, respectively, and when other process conditions were
the same as the above described conditions. The variations in
weight of the obtained CF films were examined. The results thus
obtained are shown in FIG. 11. As can be seen from the results, the
pressure dependency is substantially the same as that in Example 1,
and the variation in weight is small, 2% or less, when the process
pressure is lower than or equal to 5.5 Pa.
EXAMPLE 3
[0070] CF films were obtained using linear C.sub.5F.sub.8 gas
(which will be hereinafter referred to as <C.sub.5F.sub.8
gas>) in place of cyclic C.sub.5F.sub.8 gas as a thin-film
deposition gas when the temperature during the thin-film deposition
was set to be any one of seven temperatures, 300.degree. C.,
325.degree. C., 350.degree. C., 360.degree. C., 400.degree. C.,
420.degree. C. and 440.degree. C. The variations in weight of the
CF films obtained at the respective process temperatures were
examined. The results thus obtained are shown in FIG. 12.
[0071] In the above process, the flow rates of <C.sub.5F.sub.8
gas>, C.sub.2H.sub.4 gas and Ar gas were set to be 60 sccm, 20
sccm and 150 sccm, respectively. In addition, the microwave power
(the high-frequency power supply part 24) and the bias power (the
high-frequency power supply part 42) were set to be 2000 W and 1500
W, respectively. Moreover, the process pressure was set to be 0.1
Pa.
[0072] As can be seen from FIG. 12, the temperature dependency was
substantially the same as that in Example 1. The variation in
temperature at a process temperature of 360.degree. C. is 2.8%, and
the variation in temperature is substantially constant even if the
process temperature rises. In the case of <C.sub.5F.sub.8
gas>, the variation in weight of the CF film exceeds 2% which is
greater than that in the case of cyclic C.sub.5F.sub.8 gas used in
Example 1, although <C.sub.5F.sub.8 gas> has the same
molecular formula as that of cyclic C.sub.5F.sub.8 gas. It is
considered that the reason for this is that cyclic
C.sub.5F.sub.8gas more easily form a three-dimensional structure.
However, the variation in weight is less than 3%, and
thermostability is higher than that of C.sub.4F.sub.8 gas which
will be described later, so that <C.sub.5F.sub.8 gas> is
effectively used as a thin-film deposition gas.
[0073] In addition, CF films were deposited at a process
temperature of 400.degree. C. at various flow ratios of
<C.sub.5F.sub.8 gas> to C.sub.2H.sub.4 gas when other process
conditions were the same as the above described conditions. The
variations in weight of the obtained CF films were examined. The
results thus obtained are shown in FIG. 13. Furthermore, the flow
ratio means <C.sub.5F.sub.8>/C.sub.2H.sub.4, and the flow
rate of <C.sub.5F.sub.8 gas> was fixed to 60 sccm. When the
flow rate was less than 1, it was difficult to maintain the
deposited thin-film due to film peeling.
[0074] Moreover, CF films were deposited at a process temperature
of 400.degree. C. under various process pressures when the flow
rates of <C.sub.5F.sub.8 gas> and C.sub.2H.sub.4 gas were set
to be 60 sccm and 20 sccm, respectively, and when other process
conditions were the same as the above described conditions. The
variations in weight of the obtained CF films were examined. The
results thus obtained are shown in FIG. 14. As can be seen from the
results, the pressure dependency is different from that in Example
1, and the variation in weight is not 3% or less unless the process
pressure is 0.3 Pa or less. FIG. 15 shows the results of the mass
spectrometry for <C.sub.5F.sub.8 gas>. It is guessed from
these decomposition products that the CF film has a
three-dimensional network structure.
COMPARATIVE EXAMPLE
[0075] CF films were obtained using cyclic C.sub.4F.sub.8 gas in
place of cyclic C.sub.5F.sub.8 gas as a thin-film deposition gas.
The variations in weight of the obtained CF films were examined.
The variation in weight was very large, 3.7%. In this process, the
flow rates of C.sub.4F.sub.8 and C.sub.2H.sub.4 gases were set to
be 40 sccm and 30 sccm, respectively, and the process pressure was
set to be 0.1 Pa. In addition, the microwave power was set to be
2700 W, and other conditions were the same as those in Example
1
[0076] FIG. 16 shows the variation in weight of the thin-films
deposited at a process temperature of 400.degree. C. in Examples 1
and 3 and Comparative Example. As can be seen from these results,
the variation in weight in the case of C.sub.4F.sub.8 gas is
greater than that in the case of C.sub.5F.sub.8 gas or
<C.sub.5F.sub.8 gas>. It is guessed that the reason for this
is that the CF film obtained by causing C.sub.4F.sub.8 gas to be
decomposed and recombined as shown in FIG. 4 has many straight
chain structures to have weak C--F bonds, so that the amounts of
desorbed F, CF and CF.sub.2 are large when heat is applied thereto.
Furthermore, FIG. 17 shows the results of the mass spectrometry for
C.sub.4F.sub.8 gas. As described above, it can be seen that many
C.sub.2F.sub.4 exist as decomposition results.
[0077] In addition, the mass spectrometry was carried out at a high
temperature with respect to the CF films obtained at a process
temperature of 400.degree. C. using cyclic C.sub.5F.sub.8 gas and
C.sub.4F.sub.8 gas, respectively. Specifically, this measurement
was carried out by a mass spectrometer connected to a vacuum
vessel, in which a predetermined amount of thin-film was put and
the interior of which was heated to 425.degree. C. The results are
shown in FIGS. 18(a) and 18(b). In these drawings, the axis of
ordinates denotes a dimensionless amount corresponding to the
intensity of spectrum, and the peaks thereof denote the desorption
of the respective gases. In addition, the axis of abscissas denotes
time after the temperature rise in the vacuum vessel begins. The
temperature rises at a rate of 10.degree. C./min from room
temperature. After the temperature reaches 425.degree. C., it is
held for 30 minutes.
[0078] The amounts of F and HF desorbed from the CF films according
to the present invention shown in FIG. 8(a) are far smaller than
those in Comparative Example shown in FIG. 8b). The amounts of CF,
CF.sub.2 and CF.sub.3 shown in FIG. 8(a) are also smaller than
those in FIG. 8(b). It can be also seen from the results of the
mass spectrometry that the CF films deposited using cyclic
C.sub.5F.sub.8 gas have strong bonds and high stability.
[0079] Moreover, according to the present invention, the plasma
producing method should not be limited to the ECR, the plasma may
be produced by, e.g., a method called ICP (Inductive Coupled
Plasma) for applying electric and magnetic fields to a process gas
from a coil wound onto a dome-shaped container.
[0080] The second preferred embodiment of the present invention
will be described below.
[0081] A method for depositing an interlayer dielectric film of a
CF film on a wafer W, which is a substrate to be treated, using the
system shown in FIG. 1 will be described. First, a gate valve (not
shown) provided in the side wall of the vacuum vessel 2 is open,
and the wafer W, on which, e.g., an aluminum wiring has been
formed, is introduced from a load-lock chamber (not shown) by means
of a transport arm (not shown) to be put on the mounting table 4 to
be electrostatically absorbed by means of the electrostatic chuck
41.
[0082] Subsequently, after the gate valve is closed to seal the
interior of the vacuum vessel 2, the internal atmosphere is
exhausted by the exhaust pipes 28, and the interior of the vacuum
vessel 2 is evacuated to a predetermined degree of vacuum. Then, a
plasma producing gas, e.g., Ar gas, is introduced from the plasma
gas nozzles 31 into the first vacuum chamber 21 at a predetermined
flow rate, and a thin-film deposition gas is introduced from the
thin-film deposition gas supply part 5 into the second vacuum
chamber 22 at a predetermined flow rate.
[0083] This preferred embodiment is characterized by the thin-film
deposition gas. As the thin-film deposition gas, a gas of a
compound having a benzene ring (an aromatic compound), e.g.,
C.sub.6F.sub.6 (hexafluorobenzene), is used. Furthermore, when one
kind of C.sub.6F.sub.6 is used as the thin-film deposition gas, it
is supplied from one of the gas supply pipes 52 and 53 into the
vacuum vessel 2 via the thin-film deposition gas supply part 51.
Then, the interior of the vacuum vessel 2 is held at a
predetermined process pressure, and a bias voltage of, e.g., 13. 56
MHz and 1500 W, is applied to the mounting table 4 by means of the
high-frequency power supply part 42. In addition, the surface
temperature of the mounting table 4 is set to be about 400.degree.
C.
[0084] A high-frequency wave (a microwave) of 2.45 GHz from the
high-frequency power supply part 24 passes through the waveguide 25
to reach the ceiling of the vacuum vessel 2, and passes through the
transmission window 23 to be introduced into the first vacuum
chamber 21. On the other hand, a magnetic field extending from the
upper portion of the first vacuum chamber 21 to the lower portion
of the second vacuum chamber 22 is formed in the vacuum vessel 2 by
the electromagnetic coils 26 and 27. The intensity of the magnetic
field is, e.g., 875 gausses, in the vicinity of the lower portion
of the first vacuum chamber 21. The electron cyclotron resonance is
produced by the interaction between the magnetic field and the
microwave. By this resonance, Ar gas is activated as plasma and
enriched. The plasma flows from the first vacuum chamber 21 into
the second vacuum chamber 22 to activate C.sub.6F.sub.6, which have
been supplied thereto, to form active species to deposit a CF film
on the wafer W. Furthermore, when a device is actually produced,
the CF film is etched with a predetermined pattern, and, e.g., a W
film is embedded in a groove portion to form a W wiring.
[0085] The CF film thus deposited has a strong bond, and high
thermostability as can be seen from the results of experiment which
will be described later. The reason for this is that benzene ring
is stable since it resonates between states A and B so that each of
C--C bonds is in the intermediate state between a single bond, and
a double bond as shown in FIG. 20. Therefore, it is considered that
the C--C bonds of the benzene ring existing in the CF film, and the
bonds between C of the benzene ring and C outside the benzene ring
have strong bonding force, so that the amounts of the desorbed CF,
CF.sub.2 and CF.sub.3 are small.
[0086] FIGS. 21 and 22 show examples of benzene ring containing
compounds for use in the present invention.
EXAMPLE 1
[0087] Using a measuring device shown in FIG. 5, the variation in
weight of a thin-film at a high temperature was examined as an
index of the thermostability of the thin-film. In FIG. 5, reference
number 61 denotes a vacuum vessel, 62 denoting a heater, 63
denoting a crucible suspended from a beam of a light balance
mechanism, and 64 denoting a weight measuring part. As a measuring
method, there was adopted a method for shaving a CF film on a wafer
to put the shaven CF film in the crucible 63 to raise the
temperature in the crucible 63 to 425.degree. C. under a vacuum
atmosphere to heat the CF film for 2 hours to examine the variation
in weight in the weight measuring part 64. In the thin-film
deposition process described above in the preferred embodiment, the
flow rates of C.sub.6F.sub.8 (hexafluorobenzene) gas and Ar gases
were set to be 40 sccm and 30 sccm, respectively. In addition, the
temperature of the wafer W was set to be 400.degree. C., and the
process pressure was set to be 0.06 Pa. Moreover, the microwave
power (the power of the high-frequency power supply part 24) and
the bias power (the power of the high-frequency power supply part
42) were set to be various values. The variations in weight of the
CF films obtained on the respective conditions were examined.
Furthermore, the variation in weight means a value of
{(A-B)/A}.times.100 assuming that the weight of the thin-film in
the crucible before heating is A and the weight of the thin-film in
the crucible after heating is B.
[0088] Moreover, the mass spectrometry was carried out at a high
temperature with respect to the CF films obtained at a microwave
power of 1.0 kW at a bias power of 1.5 kW on the aforementioned
process conditions. Specifically, this measurement was carried out
by a mass spectrometer connected to a vacuum vessel, in which a
predetermined amount of thin-film was put and the interior of which
was heated to 425.degree. C. The results are shown in FIGS. 24. In
this drawing, the axis of ordinates denotes a dimensionless amount
corresponding to the intensity of spectrum, and the peaks thereof
denote the desorption of the respective gases. In addition, the
axis of abscissas denotes time after the temperature rise in the
vacuum vessel begins. The temperature rises at a rate of 10.degree.
C./min from room temperature. After the temperature reaches
425.degree. C., it is held for 30 minutes.
EXAMPLE 2
[0089] A CF film was deposited on the wafer on the same conditions
as those in Example 1, except that C.sub.7F.sub.8
(octafluorotoluene) gas was substituted for C.sub.6F.sub.6 gas, the
flow rates of C.sub.7F.sub.8 gas and Ar gas were set to be 40 sccm
and 40 sccm, respectively, the process pressure was 0.07 Pa, the
microwave power was set to be 1.0 kW and the bias power was set to
be 1.0 kW. With respect to this CF film, the variation in weight
was examined in the same manner as that in Example 1. The variation
in weight was 1.9% (see FIG. 23).
EXAMPLE 3
[0090] A CF film was deposited on the wafer on the same conditions
as those in Example 1, except that C.sub.4F.sub.8 gas and
C.sub.7H.sub.5F.sub.3 (trifluoromethylbenzene) gas were substituted
for C.sub.6F.sub.6 gas, the flow rates of C.sub.4F.sub.8 gas,
C.sub.7H.sub.5F.sub.3 gas and Ar gas were set to be 20 sccm, 20
sccm and 30 sccm, respectively, the process pressure was 0.07 Pa,
the microwave power was set to be 1.0 kW and the bias power was set
to be 1.0 kW. With respect to this CF film, the variation in weight
was examined in the same manner as that in Example 1. The variation
in weight was 2.0% (see FIG. 23).
COMPARATIVE EXAMPLE
[0091] A CF film was deposited on the wafer on the same conditions
as those in Example 1, except that C.sub.4F.sub.8 gas and
C.sub.2H.sub.4 gas were substituted for C.sub.6F.sub.6 gas, the
flow rates of C.sub.4F.sub.8 gas, C.sub.2H.sub.4 gas and Ar gas
were set to be 40 sccm, 30 sccm and 150 sccm, respectively, the
process pressure was set to be 0.22 Pa, the microwave power was set
to be 2.0 kW and the bias power was set to be 1.5 kW. With respect
to this CF film, the variation in weight was examined in the same
manner as that in Example 1. The variation in weight was 4.4% (see
FIG. 23).
[0092] Moreover, with respect to this CF film, the mass
spectrometry was carried out in the same manner as that in Example
1. The results thereof are shown in FIG. 25.
[0093] (Consideration)
[0094] As can be seen from Examples 1 and 2, when C.sub.6F.sub.6
gas or C.sub.7F.sub.8 gas is used, the variation in weight is a
level of 1%, so that thermostability is high and the amount of
degassing is small. In particular, when C.sub.6F.sub.6 gas is used,
thermostability is very high. As can be seen from the comparison of
FIG. 24 with FIG. 25, when C.sub.6F.sub.6 gas is used, the amounts
of the desorbed CF, CF.sub.2 and CF.sub.3 are smaller than those
when C.sub.4F.sub.8 gas and C.sub.2H.sub.4 gas are used. This meets
the guess that C--C bonds are difficult to be cut when a material
gas of an aromatic compound is used as described above. It is
considered that the decomposition products of C.sub.6F.sub.6 gas
are C.sub.6F.sub.6, C.sub.5F.sub.3, C.sub.3F.sub.3 and so forth
which have double bonds. The recombination product thereof has a
three-dimensional structure and-strong bonds. Even at a high
temperature, the bonds of the recombination product are difficult
to be cut, so that the amount of degassing is small.
[0095] It is guessed that the reason why the variations in weight
in Examples 3 and 4 is a level of 2%, which is greater than those
in Examples 1 and 2 although it is less than that in Comparative
Example, is as follows. That is, if C.sub.7F.sub.8 gas or
C.sub.7H.sub.5F.sub.3 gas is used alone, F is insufficient, so that
C.sub.4F.sub.8 gas is added. The network structure is reduced by
the thin-film deposited on the basis of the decomposition products
of C.sub.7F.sub.8 gas, so that the C--C bonds are cut to be
desorbed as CF, CF.sub.2 and CF.sub.3. As a result, the variation
in weight is greater than that when C.sub.6F.sub.6 gas or
C.sub.7F.sub.8 gas is used.
[0096] The decomposition products of C.sub.6F.sub.6, C.sub.7F.sub.8
and C.sub.8H.sub.4F.sub.6 (1, 4-bistrifluoromethylbenzene) are
vaporized under a reduced pressure of 0.002 Pa, and the vaporized
decomposition products were analyzed by means of a mass
spectrometer. The obtained results are shown in FIGS. 26 through
28. It can be seen from these results that many benzene ring
containing components exist as decomposition products, so that it
can be guessed that a stable CF film having a network structure is
produced.
[0097] Moreover, according to the present invention, the plasma
producing method should not be limited to the ECR, the plasma may
be produced by, e.g., a method called ICP (Inductive Coupled
Plasma) for applying electric and magnetic fields to a process gas
from a coil wound onto a dome-shaped container.
[0098] The first and second preferred embodiments of the present
invention have been described above. According to these preferred
embodiments, it is possible to produce a CF film which has high
thermostability and a small amount of desorbed F gas. Therefore, if
this CF film is used as, e.g., an interlayer dielectric film of a
semiconductor device, it is possible to prevent the corrosion of a
metal wiring, the swell of an aluminum wiring and the crack of the
film. Since CF films have been widely noticed as insulator films
having a small relative dielectric constant and since the scale
down and high integration of semiconductor devices have been
required, the present invention is effective in the practical use
of CF films as insulator films.
* * * * *