U.S. patent application number 09/834645 was filed with the patent office on 2001-11-01 for pattern forming material and pattern forming method.
This patent application is currently assigned to Matsushita Electric Industrial Co., Ltd.. Invention is credited to Endo, Masayuki, Matsuo, Takahiro, Shiri, Masamitsu, Tsunooka, Masahiro.
Application Number | 20010036599 09/834645 |
Document ID | / |
Family ID | 12516064 |
Filed Date | 2001-11-01 |
United States Patent
Application |
20010036599 |
Kind Code |
A1 |
Matsuo, Takahiro ; et
al. |
November 1, 2001 |
Pattern forming material and pattern forming method
Abstract
A pattern forming material includes a binary copolymer
represented by the following general formula or a ternary or higher
copolymer obtained by further polymerizing the binary copolymer
with another group: 1 wherein R.sub.1 indicates a hydrogen atom or
an alkyl group; R.sub.2 and R.sub.3 independently indicate a
hydrogen atom, an alkyl group, a phenyl group or an alkenyl group
or together indicate a cyclic alkyl group, a cyclic alkenyl group,
a cyclic alkyl group having a phenyl group or a cyclic alkenyl
group having a phenyl group; R.sub.4 indicates a hydrogen atom or
an alkyl group; x satisfies a relationship of 0<x<1; and y
satisfies a relationship of 0<y<1.
Inventors: |
Matsuo, Takahiro; (Kyoto,
JP) ; Endo, Masayuki; (Osaka, JP) ; Shiri,
Masamitsu; (Osaka, JP) ; Tsunooka, Masahiro;
(Osaka, JP) |
Correspondence
Address: |
McDERMOTT, WILL & EMERY
600 13th Street, N.W.
Washington
DC
20005-3096
US
|
Assignee: |
Matsushita Electric Industrial Co.,
Ltd.
Osaka
JP
|
Family ID: |
12516064 |
Appl. No.: |
09/834645 |
Filed: |
April 16, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09834645 |
Apr 16, 2001 |
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09551656 |
Apr 18, 2000 |
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09551656 |
Apr 18, 2000 |
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09326541 |
Jun 7, 1999 |
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6120974 |
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09326541 |
Jun 7, 1999 |
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08805702 |
Feb 25, 1997 |
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5965325 |
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Current U.S.
Class: |
430/287.1 ;
430/195; 430/270.1; 430/313; 430/314; 430/323; 430/324; 526/262;
526/282; 526/287 |
Current CPC
Class: |
G03F 7/0045 20130101;
G03F 7/265 20130101; G03F 7/039 20130101 |
Class at
Publication: |
430/287.1 ;
430/195; 430/314; 430/313; 430/323; 430/324; 430/270.1; 526/262;
526/287; 526/282 |
International
Class: |
G03F 007/039; G03F
007/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 26, 1996 |
JP |
8-038100 |
Claims
What is claimed is:
1. A pattern forming material comprising a copolymer including a
first group for generating a base through irradiation with an
energy beam and a second group having an acidic property.
2. The pattern forming material of claim 1, wherein said second
group is a group including a sulfonic acid group.
3. The pattern forming material of claim 1, wherein said copolymer
is a binary copolymer represented by the following general formula
or a ternary or higher copolymer obtained by further polymerizing
said binary copolymer with another group: 20wherein R.sub.1
indicates a hydrogen atom or an alkyl group; R.sub.2 and R.sub.3
independently indicate a hydrogen atom, an alkyl group, a phenyl
group or an alkenyl group, or together indicate a cyclic alkyl
group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl
group or a cyclic alkenyl group having a phenyl group; R.sub.4
indicates a hydrogen atom or an alkyl group; x satisfies a
relationship of 0<x<1; and y satisfies a relationship of
0<y<1.
4. A pattern forming material comprising a copolymer including a
first group for generating an acid through irradiation with an
energy beam and a second group having a basic property.
5. The pattern forming material of claim 4, wherein said first
group is a group for generating sulfonic acid.
6. The pattern forming material of claim 4, wherein said copolymer
is a binary copolymer represented by the following general formula
or a ternary or higher copolymer obtained by further polymerizing
said binary copolymer with another group: 21wherein R.sub.5
indicates a hydrogen atom or an alkyl group; R.sub.6 and R.sub.7
independently indicate a hydrogen atom, an alkyl group, a phenyl
group or an alkenyl group, or together indicate a cyclic alkyl
group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl
group or a cyclic alkenyl group having a phenyl group; R.sub.8
indicates a hydrogen atom or an alkyl group; x satisfies a
relationship of 0<x<1; and y satisfies a relationship of
0<y<1.
7. A pattern forming material comprising a copolymer including: a
first group for generating an acid through irradiation with a first
energy beam having a first energy band; and a second group for
generating a base through irradiation with a second energy beam
having a second energy band different from said first energy
band.
8. The pattern forming material of claim 7, wherein said first
group is a group for generating sulfonic acid.
9. The pattern forming material of claim 7, wherein said copolymer
is a binary copolymer represented by the following general formula
or a ternary or higher copolymer obtained by further polymerizing
said binary copolymer with another group: 22wherein R.sub.9
indicates a hydrogen atom or an alkyl group; R.sub.10 and R.sub.11
independently indicate a hydrogen atom, an alkyl group, a phenyl
group or an alkenyl group, or together indicate a cyclic alkyl
group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl
group or a cyclic alkenyl group having a phenyl group; R.sub.12
indicates a hydrogen atom or an alkyl group; R.sub.13 and R.sub.14
independently indicate a hydrogen atom, an alkyl group, a phenyl
group or an alkenyl group, or together indicate a cyclic alkyl
group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl
group or a cyclic alkenyl group having a phenyl group; x satisfies
a relationship of 0<x<1; and y satisfies a relationship of
0<y<1.
10. A pattern forming method comprising: a first step of forming a
resist film by coating a semiconductor substrate with a pattern
forming material including a copolymer having a first group for
generating a base through irradiation with an energy beam and a
second group having an acidic property; a second step of
selectively irradiating said resist film with said energy beam by
using a mask having a desired pattern, generating said base in an
exposed area on said resist film and neutralizing said generated
base with said second group; a third step of supplying metal
alkoxide onto said resist film and forming a metal oxide film on a
surface of an unexposed area on said resist film; and a fourth step
of forming a resist pattern by dry-etching said resist film by
using said metal oxide film as a mask.
11. The pattern forming method of claim 10, wherein said third step
includes a step of allowing said unexposed area on said resist film
to adsorb water.
12. The pattern forming method of claim 10, wherein said second
group is a group including a sulfonic acid group.
13. The pattern forming method of claim 10, wherein said copolymer
is a binary copolymer represented by the following general formula
or a ternary or higher copolymer obtained by further polymerizing
said binary copolymer with another group: 23wherein R.sub.1
indicates a hydrogen atom or an alkyl group; R.sub.2 and R.sub.3
independently indicate a hydrogen atom, an alkyl group, a phenyl
group or an alkenyl group, or together indicate a cyclic alkyl
group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl
group or a cyclic alkenyl group having a phenyl group; R.sub.4
indicates a hydrogen atom or an alkyl group; x satisfies a
relationship of 0<x<1; and y satisfies a relationship of
0<y<1.
14. A pattern forming method comprising: a first step of forming a
resist film by coating a semiconductor substrate with a pattern
forming material including a copolymer having a first group for
generating an acid through irradiation with an energy beam and a
second group having a basic property; a second step of selectively
irradiating said resist film with said energy beam by using a mask
having a desired pattern, generating said acid in an exposed area
on said resist film and neutralizing said generated acid with said
second group; a third step of supplying metal alkoxide onto said
resist film and forming a metal oxide film on a surface of an
unexposed area on said resist film; and a fourth step of forming a
resist pattern by dry-etching said resist film by using said metal
oxide film as a mask.
15. The pattern forming method of claim 14, wherein said third step
includes a step of allowing said unexposed area on said resist film
to adsorb water.
16. The pattern forming method of claim 14, wherein said first
group is a group for generating sulfonic acid.
17. The pattern forming method of claim 14, wherein said copolymer
is a binary copolymer represented by the following general formula
or a ternary or higher copolymer obtained by further polymerizing
said binary copolymer with another group: 24wherein R.sub.5
indicates a hydrogen atom or an alkyl group; R.sub.6 and R.sub.7
independently indicate a hydrogen atom, an alkyl group, a phenyl
group or an alkenyl group, or together indicate a cyclic alkyl
group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl
group or a cyclic alkenyl group having a phenyl group; R.sub.8
indicates a hydrogen atom or an alkyl group; x satisfies a
relationship of 0<x<1; and y satisfies a relationship of
0<y<1.
18. A pattern forming method comprising: a first step of forming a
resist film by coating a semiconductor substrate with a pattern
forming material including a copolymer having a first group for
generating an acid through irradiation with a first energy beam
having a first energy band and a second group for generating a base
through irradiation with a second energy beam having a second
energy band different from said first energy band; a second step of
selectively irradiating said resist film with said first energy
beam by using a mask having a desired pattern, and generating said
acid in an exposed area of said first energy beam on said resist
film; a third step of irradiating an entire surface of said resist
film with said second energy beam, generating said base on the
entire surface of said resist film, and neutralizing said generated
base with said acid generated in said exposed area of said first
energy beam on said resist film; a fourth step of supplying metal
alkoxide onto said resist film and forming a metal oxide film on a
surface of an unexposed area of said first energy beam on said
resist film; and a fifth step of forming a resist pattern by
dry-etching said resist film by using said metal oxide film as a
mask.
19. The pattern forming method of claim 18, wherein said first
group is a group for generating sulfonic acid.
20. The pattern forming method of claim 18, wherein said fourth
step includes a step of allowing said unexposed area on said resist
film to adsorb water.
21. The pattern forming method of claim 18, wherein said copolymer
is a binary copolymer represented by the following general formula
or a ternary or higher copolymer obtained by further polymerizing
said binary copolymer with another group: 25wherein R.sub.9
indicates a hydrogen atom or an alkyl group; R.sub.10 and R.sub.11
independently indicate a hydrogen atom, an alkyl group, a phenyl
group or an alkenyl group, or together indicate a cyclic alkyl
group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl
group or a cyclic alkenyl group having a phenyl group; R.sub.12
indicates a hydrogen atom or an alkyl group; R.sub.13 and R.sub.14
independently indicate a hydrogen atom, an alkyl group, a phenyl
group or an alkenyl group, or together indicate a cyclic alkyl
group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl
group or a cyclic alkenyl group having a phenyl group; x satisfies
a relationship of 0<x<1; and y satisfies a relationship of
0<y<1.
22. A pattern forming method comprising: a first step of forming a
resist film by coating a semiconductor substrate with a pattern
forming material including a copolymer having a first group for
generating a base through irradiation with a first energy beam
having a first energy band and a second group for generating an
acid through irradiation with a second energy beam having a second
energy band different from said first energy band; a second step of
selectively irradiating said resist film with said first energy
beam by using a mask having a desired pattern, and generating said
base in an exposed area of said first energy beam on said resist
film; a third step of irradiating an entire surface of said resist
film with said second energy beam, generating said acid on the
entire surface of said resist film, and neutralizing said generated
acid with said base generated in said exposed area of said first
energy beam on said resist film; a fourth step of supplying metal
alkoxide onto said resist film and forming a metal oxide film on a
surface of an unexposed area of said first energy beam on said
resist film; and a fifth step of forming a resist pattern by
dry-etching said resist film by using said metal oxide film as a
mask.
23. The pattern forming method of claim 22, wherein said second
group is a group for generating sulfonic acid.
24. The pattern forming method of claim 22, wherein said fourth
step includes a step of allowing said unexposed area on said resist
film to adsorb water.
25. The pattern forming method of claim 22, wherein said copolymer
is a binary copolymer represented by the following general formula
or a ternary or higher copolymer obtained by further polymerizing
said binary copolymer with another group: 26wherein R.sub.9
indicates a hydrogen atom or an alkyl group; R.sub.10 and R.sub.11
independently indicate a hydrogen atom, an alkyl group, a phenyl
group or an alkenyl group, or together indicate a cyclic alkyl
group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl
group or a cyclic alkenyl group having a phenyl group; R.sub.12
indicates a hydrogen atom or an alkyl group; R.sub.13 and R.sub.14
independently indicate a hydrogen atom, an alkyl group, a phenyl
group or an alkenyl group, or together indicate a cyclic alkyl
group, a cyclic alkenyl group, a cyclic alkyl group having a phenyl
group or a cyclic alkenyl group having a phenyl group; x satisfies
a relationship of 0<x<1; and y satisfies a relationship of
0<y<1.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a fine-line pattern forming
method for use in a manufacturing process for a semiconductor IC
device and the like, and a material for forming a pattern used in
the pattern forming method.
[0002] In the manufacture of ICs, LSIs and the like, a pattern is
conventionally formed through photolithography using UV, in which a
light source with a shorter wavelength has become mainly used in
accordance with refinement of a semiconductor device. Recently, a
surface imaging process using dry development has been developed in
order to increase the depth of focus and improve practical
resolution in using a light source with a shorter wavelength.
[0003] As an example of the surface imaging process, U.S. Pat. No.
5,278,029 discloses a method in which, after selectively forming a
polysiloxane film on the surface of a resist film of a resist
material which can generate an acid through exposure, the resist
film is dry etched by using the polysiloxane film as a mask, so as
to form a resist pattern.
[0004] Now, this conventional method of forming the resist pattern
will be described with reference to FIGS. 5(a) through 5(d).
[0005] In this method, a copolymer of
1,2,3,4-tetrahydronaphthyridinenimin- o-p-styrene sulfonate (NISS)
and methyl methacrylate (MMA) is used as the resist material for
generating an acid through exposure.
[0006] First, as is shown in FIG. 5(a), a resist film 401, which
generates an acid through exposure, coated on a semiconductor
substrate 400 is irradiated with a KrF excimer laser 404 by using a
mask 403, and thus, the acid is generated in an exposed area 401a
of the resist film 401. Owing to this acid, the exposed area 401a
is changed to be hydrophilic, so that water in air can be easily
adsorbed by the exposed area 401a. As a result, a thin water
absorbing layer 405 is formed in the vicinity of the surface of the
exposed area 401a as is shown in FIG. 5(b).
[0007] Next, when an alkoxysilane gas 406 is introduced onto the
surface of the resist film 401, the acid generated on the surface
of the exposed area 401a works as a catalyst, so that alkoxysilane
is hydrolyzed and dehydrated. As a result, an oxide film 407 is
formed on the surface of the exposed area 401a as is shown in FIG.
5(c). Subsequently, when the resist film 401 is dry etched by RIE
using O.sub.2 plasma 408 by using the oxide film 407 as a mask, a
fine-line resist pattern 409 is formed as is shown in FIG.
5(d).
[0008] This pattern forming method thus adopts a negative type
lithography process for forming a resist pattern in an exposed
area, in which the acid generated in the exposed area of the resist
film is used as the catalyst for selectively forming the oxide film
in the exposed area and the oxide film is used as a mask in the dry
etching for forming the resist pattern.
[0009] The negative type lithography process has the following
problems in, for example, forming a contact hole for connecting
multilayered interconnections of an IC:
[0010] First, usage of a mask generally adopted in pattern exposure
can cause the following problem: In the lithography for forming a
contact hole, the aperture ratio of the mask is very high when the
negative lithography process is used. Specifically, while a light
shielding film against exposing light is formed merely in a portion
corresponding to the contact hole on the mask, the light shielding
film is removed and quartz of the mask substrate is bare in the
other portion excluding the contact hole in order to transmit the
exposing light. Since the area occupied by all the contact holes in
the entire area of a semiconductor chip is generally very small,
the proportion of the area occupied by the bare quartz to the area
of the light shielding film on the mask becomes high, namely, the
aperture ratio of the mask becomes high.
[0011] When the aperture ratio of the mask is high, the effect of
ambient dusts is increased. Specifically, dusts adhered to the
light shielding film on the mask scarcely affect the process, but
those adhered to the transparent portion of the mask change this
portion into a light shielding portion. When the exposure is
effected by using the mask to which dusts are thus adhered, a
pattern defect is caused in the portion to which the dusts are
adhered. In this manner, since the aperture ratio of the mask is
high in the negative type lithography process, the process can be
easily affected by dusts, resulting in easily decreasing the
yield.
[0012] Secondly, in the lithography process for forming a contact
hole, a half-tone type mask can be used for the purpose of
increasing the depth of focus. However, the effect of increasing
the depth of focus can be attained merely in a positive type
lithography but cannot be attained in the negative type
lithography. Accordingly, in the formation of a contact hole, the
depth of focus is smaller in the negative type process than in the
positive type process.
[0013] The occurrence of these first and second problems are not
limited to the formation of a contact hole, but can be caused in
the cases where a mask having a larger area of the transparent
portion is used and where the depth of focus is desired to be
increased.
SUMMARY OF THE INVENTION
[0014] In view of the aforementioned conventional problems, the
object of the invention is realizing a positive type surface
imaging process replaceable with the negative type surface imaging
process.
[0015] In order to achieve this object, a resist film including an
acidic or a basic group is selectively irradiated with an energy
beam in this invention, so that a basic or an acidic group having
the reverse property to that of the group included in the resist
film can be generated in an exposed area. Alternatively, after
generating an acidic or a basic group in an exposed area by
selectively irradiating a resist film with an energy beam, the
entire surface of the resist film is irradiated with another energy
beam, so that a basic or an acidic group having the reverse
property to that of the group generated in the exposed area can be
generated on the entire surface of the resist film. Thus,
neutralization is effected in the exposed area of the resist film,
and in an unexposed area of the resist film, the acidic or the
basic group works as a catalyst for forming an oxide film. In this
manner, a positive type surface imaging process, which cannot be
attained by the conventional method, can be realized by this
invention.
[0016] The first pattern forming material of this invention
comprises a copolymer including a first group for generating a base
through irradiation with an energy beam and a second group having
an acidic property.
[0017] When the resist film formed out of the first pattern forming
material is selectively irradiated with the energy beam, the first
group is dissolved into the base in the exposed area on the resist
film, so that the generated base is neutralized with the second
group having the acidic property, while the unexposed area on the
resist film remains to be acidic. Accordingly, since merely the
unexposed area on the resist film can selectively retain its acidic
property, the positive type surface imaging process can be
realized.
[0018] The second group in the first pattern forming material is
preferably a group including a sulfonic acid group. In this case,
owing to the strong acidic property of sulfonic acid, sulfonic acid
can exhibit its strong catalytic function in the formation of the
metal oxide film in the unexposed area on the resist film.
Therefore, the strong acidic property can be selectively retained
merely in the unexposed area on the resist film.
[0019] The copolymer in the first pattern forming material is
preferably a binary copolymer represented by the following general
formula or a ternary or higher copolymer obtained by further
polymerizing the binary copolymer with another group: 2
[0020] wherein R.sub.1 indicates a hydrogen atom or an alkyl group;
R.sub.2 and R.sub.3 independently indicate a hydrogen atom, an
alkyl group, a phenyl group or an alkenyl group, or together
indicate a cyclic alkyl group, a cyclic alkenyl group, a cyclic
alkyl group having a phenyl group or a cyclic alkenyl group having
a phenyl group; R.sub.4 indicates a hydrogen atom or an alkyl
group; x satisfies a relationship of 0<x<1; and y satisfies a
relationship of 0<y<1.
[0021] In this case, since sulfonic acid can exhibit its strong
catalytic function in the formation of the metal oxide film in the
unexposed area on the resist film, the strong acidic property can
be selectively retained in the unexposed area on the resist film.
On the other hand, in the exposed area on the resist film, since
amine having a strong basic property is generated, sulfonic acid
having a strong acidic property can be completely neutralized.
Accordingly, the strong acidic property can be selectively retained
merely in the unexposed area on the resist film.
[0022] The second pattern forming material of this invention
comprises a copolymer including a first group for generating an
acid through irradiation with an energy beam and a second group
having a basic property.
[0023] When the resist film formed out of the second pattern
forming material is selectively irradiated with the energy beam,
the first group is dissolved into the acid in the exposed area on
the resist film, so that the generated acid can be neutralized with
the second group having the basic property, while the unexposed
area on the resist film remains to be basic. Accordingly, merely
the unexposed area on the resist film can selectively retain the
basic property, resulting in realizing the positive type surface
imaging process.
[0024] The first group in the second pattern forming material is
preferably a group for generating sulfonic acid. In this case,
owing to the strong acidic property of sulfonic acid, the exposed
area on the resist film can be completely neutralized, while the
unexposed area on the resist film remains to be basic. Accordingly,
the unexposed area of the resist film can selectively retain the
basic property.
[0025] The copolymer in the second pattern forming material is
preferably a binary copolymer represented by the following general
formula or a ternary or higher copolymer obtained by further
polymerizing the binary copolymer with another group: 3
[0026] wherein R.sub.5 indicates a hydrogen atom or an alkyl group;
R.sub.6 and R.sub.7 independently indicate a hydrogen atom, an
alkyl group, a phenyl group or an alkenyl group, or together
indicate a cyclic alkyl group, a cyclic alkenyl group, a cyclic
alkyl group having a phenyl group or a cyclic alkenyl group having
a phenyl group; R.sub.8 indicates a hydrogen atom or an alkyl
group; x satisfies a relationship of 0<x<1; and y satisfies a
relationship of 0<y<1.
[0027] In this case, amine can exhibit its strong catalytic
function in the formation of the metal oxide film in the unexposed
area on the resist film, so that the unexposed area on the resist
film can selectively retain the strong basic property. On the other
hand, in the exposed area of the resist film, since sulfonic acid
having a strong acidic property is generated, amine having a strong
basic property can be completely neutralized. Accordingly, merely
the unexposed area on the resist film can selectively retain the
strong basic property.
[0028] The third pattern forming material of this invention
comprises a copolymer including a first group for generating an
acid through irradiation with a first energy beam having a first
energy band; and a second group for generating a base through
irradiation with a second energy beam having a second energy band
different from the first energy band.
[0029] In the resist film formed out of the third pattern forming
material, the acid is generated through the irradiation with the
first energy beam, and the base is generated through the
irradiation with the second energy beam. Accordingly, when the
pattern exposure of the resist film using the first energy beam is
effected and then the entire surface exposure using the second
energy beam is effected, in the exposed area of the first energy
beam on the resist film, the acid generated through the pattern
exposure using the first energy beam is neutralized with the base
generated through the entire surface exposure using the second
energy beam. On the other hand, the unexposed area of the first
energy beam on the resist film attains a basic property through the
entire surface exposure using the second energy beam. Contrarily,
when the pattern exposure of the resist film using the second
energy beam is effected and then the entire surface exposure using
the first energy beam is effected, in the exposed area of the
second energy beam on the resist film, the base generated through
the pattern exposure using the second energy beam is neutralized
with the acid generated through the entire surface exposure using
the first energy beam. On the other hand, the unexposed area of the
second energy beam on the resist film attains an acidic property
through the entire surface exposure using the first energy beam.
Accordingly, the positive type surface imaging process can be
realized.
[0030] Furthermore, since the third pattern forming material
comprises the copolymer including the first group for generating
the acid through the irradiation with the first energy beam and the
second group for generating the base through the irradiation with
the second energy beam, the acid or the base cannot be generated
until the irradiation with the energy beam, namely, the resist film
remains to be neutral until the irradiation with the energy beam.
Accordingly, the pattern forming material can be prevented from
being changed in its property by an acid or a base during
pre-baking, resulting in forming a stable resist film.
[0031] The first group in the third pattern forming material is
preferably a group for generating sulfonic acid. In this case, when
the pattern exposure is effected by using the first energy beam,
owing to the strong acidic property of sulfonic acid, the exposed
area of the first energy beam on the resist film can be completely
neutralized, while the unexposed area of the first energy beam on
the resist film retains the basic property. Accordingly, merely the
unexposed area of the first energy beam on the resist film can
selectively retain the basic property. Contrarily, when the pattern
exposure is effected by using the second energy beam, the unexposed
area of the second energy beam on the resist film can exhibit a
strong catalytic function in the formation of the oxide film.
Accordingly, merely the unexposed area of the second energy beam on
the resist film can selectively retain the strong acidic
property.
[0032] The copolymer in the third pattern forming material is
preferably a binary copolymer represented by the following general
formula or a ternary or higher copolymer obtained by further
polymerizing the binary copolymer with another group: 4
[0033] wherein R.sub.9 indicates a hydrogen atom or an alkyl group;
R.sub.10 and R.sub.11 independently indicate a hydrogen atom, an
alkyl group, a phenyl group or an alkenyl group, or together
indicate a cyclic alkyl group, a cyclic alkenyl group, a cyclic
alkyl group having a phenyl group or a cyclic alkenyl group having
a phenyl group; R.sub.12 indicates a hydrogen atom or an alkyl
group; R.sub.13 and R.sub.14 independently indicate a hydrogen
atom, an alkyl group, a phenyl group or an alkenyl group, or
together indicate a cyclic alkyl group, a cyclic alkenyl group, a
cyclic alkyl group having a phenyl group or a cyclic alkenyl group
having a phenyl group; x satisfies a relationship of 0<x<1;
and y satisfies a relationship of 0<y<1.
[0034] In this case, sulfonic acid having a strong acidic property
is generated through the irradiation of the resist film with the
first energy beam, and amine having a strong basic property is
generated through the irradiation with the second energy beam.
Therefore, when the pattern exposure is effected by using the first
energy beam, the unexposed area of the first energy beam on the
resist film retains the strong basic property, while the exposed
area of the first energy beam on the resist film can be completely
neutralized. Contrarily, when the pattern exposure is effected by
using the second energy beam, the unexposed area of the second
energy beam on the resist film retains the strong acidic property,
while the exposed area of the second energy beam on the resist film
can be completely neutralized.
[0035] The first pattern forming method of this invention comprises
a first step of forming a resist film by coating a semiconductor
substrate with a pattern forming material including a copolymer
having a first group for generating a base through irradiation with
an energy beam and a second group having an acidic property; a
second step of selectively irradiating the resist film with the
energy beam by using a mask having a desired pattern, generating
the base in an exposed area on the resist film and neutralizing the
generated base with the second group; a third step of supplying
metal alkoxide onto the resist film and forming a metal oxide film
on a surface of an unexposed area on the resist film; and a fourth
step of forming a resist pattern by dry-etching the resist film by
using the metal oxide film as a mask.
[0036] According to the first pattern forming method, through the
irradiation of the resist film with the energy beam, the generated
base is neutralized with the second group having the acidic
property in the exposed area on the resist film, while the
unexposed area on the resist film remains to be acidic When the
metal alkoxide is supplied to the resist film, the metal oxide film
cannot be formed in the exposed area because the exposed area on
the resist film has been neutralized, but the metal oxide film is
selectively formed in the unexposed area on the resist film.
Accordingly, through the dry etching of the resist film using the
metal oxide film as a mask, it is possible to form a fine-line
positive type resist pattern having a satisfactory shape.
[0037] Furthermore, according to the first pattern forming method,
the acid works as the catalyst in the formation of the metal oxide
film in the unexposed area on the resist film, and hence, the
resultant metal oxide film can attain a high density and sufficient
strength.
[0038] In the first pattern forming method, the third step
preferably includes a step of allowing the unexposed area on the
resist film to adsorb water. In this case, since water can be
diffused into a deep portion from the surface of the unexposed area
on the resist film, the metal oxide film formed on the surface of
the unexposed area on the resist film can attain a large
thickness.
[0039] In the first pattern forming method, the second group is
preferably a group including a sulfonic acid group. In this case,
owing to the strong acidic property of sulfonic acid, it is
possible to form the metal oxide film having a sufficient density
in the unexposed area on the resist film by using the strong
catalytic function of sulfonic acid. As a result, the selectivity
in the dry etching can be improved. Thus, it is possible to form a
more fine-line positive type resist pattern having a satisfactory
shape.
[0040] The copolymer used in the first pattern forming method is
preferably a binary copolymer represented by the following general
formula or a ternary or higher copolymer obtained by further
polymerizing the binary copolymer with another group: 5
[0041] wherein R.sub.1 indicates a hydrogen atom or an alkyl group;
R.sub.2 and R.sub.3 independently indicate a hydrogen atom, an
alkyl group, a phenyl group or an alkenyl group, or together
indicate a cyclic alkyl group, a cyclic alkenyl group, a cyclic
alkyl group having a phenyl group or a cyclic alkenyl group having
a phenyl group; R.sub.4 indicates a hydrogen atom or an alkyl
group; x satisfies a relationship of 0<x<1; and y satisfies a
relationship of 0<y<1.
[0042] In this case, since sulfonic acid can exhibit its strong
catalytic function in the formation of the metal oxide film in the
unexposed area on the resist film, the unexposed area on the resist
film can selectively retain the strong acidic property. Therefore,
the metal oxide film having a sufficient density can be formed by
supplying the metal alkoxide. Furthermore, in the exposed area on
the resist film, since amine having a strong basic property is
generated, sulfonic acid having a strong acidic property can be
completely neutralized. Therefore, the metal oxide film cannot be
formed in the exposed area. In this manner, the selectivity in the
dry etching is high, and hence, it is possible to form a more
fine-line positive type resist pattern having a satisfactory
shape.
[0043] The second pattern forming method of this invention
comprises a first step of forming a resist film by coating a
semiconductor substrate with a pattern forming material including a
copolymer having a first group for generating an acid through
irradiation with an energy beam and a second group having a basic
property; a second step of selectively irradiating the resist film
with the energy beam by using a mask having a desired pattern,
generating the acid in an exposed area on the resist film and
neutralizing the generated acid with the second group; a third step
of supplying metal alkoxide onto the resist film and forming a
metal oxide film on a surface of an unexposed area on the resist
film; and a fourth step of forming a resist pattern by dry-etching
the resist film by using the metal oxide film as a mask.
[0044] According to the second pattern forming method, through the
irradiation of the resist film with the energy beam, the generated
acid is neutralized with the second group having the basic property
in the exposed area on the resist film, while the unexposed area on
the resist film remains to be basic. When the metal alkoxide is
supplied to the resist film, the metal oxide film cannot be formed
in the exposed area because the exposed area on the resist film has
been neutralized, but the metal oxide film is selectively formed in
the unexposed area on the resist film. Accordingly, through the dry
etching of the resist film using the metal oxide film as a mask, it
is possible to form a fine-line positive type resist pattern having
a satisfactory shape.
[0045] Furthermore, according to the second pattern forming method,
the base works as a catalyst in the formation of the metal oxide
film in the unexposed area on the resist film. Therefore, the speed
for forming the metal oxide film can be improved, resulting in
improving throughput.
[0046] In the second pattern forming method, the third step
preferably includes a step of allowing the unexposed area on the
resist film to adsorb water. In this case, since water is diffused
into a deep portion from the surface of the unexposed area on the
resist film, the metal oxide film formed in the unexposed area on
the resist film can attain a large thickness.
[0047] In the second pattern forming method, the first group is
preferably a group for generating sulfonic acid. In this case,
owing to the strong acidic property of sulfonic acid, the exposed
area on the resist film can be completely neutralized, while the
unexposed area on the resist film retains the basic property.
Therefore, the metal oxide film can be formed merely in the
unexposed area on the resist film with high selectivity.
Accordingly, it is possible to form a more fine-line positive
resist pattern having a satisfactory shape.
[0048] The copolymer used in the second pattern forming method is
preferably a binary copolymer represented by the following general
formula or a ternary or higher copolymer obtained by further
polymerizing the binary copolymer with another group: 6
[0049] wherein R.sub.5 indicates a hydrogen atom or an alkyl group;
R.sub.6 and R.sub.7 independently indicate a hydrogen atom, an
alkyl group, a phenyl group or an alkenyl group, or together
indicate a cyclic alkyl group, a cyclic alkenyl group, a cyclic
alkyl group having a phenyl group or a cyclic alkenyl group having
a phenyl group; R.sub.8 indicates a hydrogen atom or an alkyl
group; x satisfies a relationship of 0<x<1; and y satisfies a
relationship of 0<y<1.
[0050] In this case, in the unexposed area on the resist film,
amine exhibits its strong catalytic function, and hence, the metal
oxide film with a sufficient density can be formed. On the other
hand, in the exposed area on the resist film, since sulfonic acid
having a strong acidic property is generated, amine having a strong
basic property can be completely neutralized. As a result, the
selectivity in the dry etching is very high, and it is possible to
form a more fine-line positive resist pattern having a satisfactory
shape.
[0051] The third pattern forming method of this invention comprises
a first step of forming a resist film by coating a semiconductor
substrate with a pattern forming material including a copolymer
having a first group for generating an acid through irradiation
with a first energy beam having a first energy band and a second
group for generating a base through irradiation with a second
energy beam having a second energy band different from the first
energy band; a second step of selectively irradiating the resist
film with the first energy beam by using a mask having a desired
pattern, and generating the acid in an exposed area of the first
energy beam on the resist film; a third step of irradiating an
entire surface of the resist film with the second energy beam,
generating the base on the entire surface of the resist film, and
neutralizing the generated base with the acid generated in the
exposed area of the first energy beam on the resist film; a fourth
step of supplying metal alkoxide onto the resist film and forming a
metal oxide film on a surface of an unexposed area of the first
energy beam on the resist film; and a fifth step of forming a
resist pattern by dry-etching the resist film by using the metal
oxide film as a mask.
[0052] According to the third pattern forming method, in the
exposed area of the first energy beam on the resist film, since the
acid generated through the pattern exposure using the first energy
beam is neutralized with the base generated through the entire
surface exposure using the second energy beam, the metal oxide film
cannot be formed in the exposed area. On the other hand, in the
unexposed area of the first energy beam on the resist film, since
the base is generated through the entire surface exposure using the
second energy beam, the metal oxide film can be formed owing to the
catalytic function of the base by supplying the metal alkoxide to
the resist film. Accordingly, through the dry etching of the resist
film using the metal oxide film as a mask, a positive type resist
pattern can be formed.
[0053] Furthermore, according to the third pattern forming method,
since the base works as the catalyst in the formation of the metal
oxide film in the unexposed area of the first energy beam on the
resist film, the speed for forming the metal oxide film can be
improved, resulting in improving the throughput.
[0054] In the third pattern forming method, the first group is
preferably a group for generating sulfonic acid. In this case,
owing to the strong acidic property of sulfonic acid, the exposed
area of the first energy beam on the resist film can be completely
neutralized, while the unexposed area of the first energy beam on
the resist film retains the basic property. Accordingly, the metal
oxide film can be formed merely in the unexposed area of the first
energy beam on the resist film with very high selectivity. As a
result, it is possible to form a more fine-line positive type
resist pattern having a satisfactory shape.
[0055] The fourth pattern forming method of this invention
comprises a first step of forming a resist film by coating a
semiconductor substrate with a pattern forming material including a
copolymer having a first group for generating a base through
irradiation with a first energy beam having a first energy band and
a second group for generating an acid through irradiation with a
second energy beam having a second energy band different from the
first energy band; a second step of selectively irradiating the
resist film with the first energy beam by using a mask having a
desired pattern, and generating the base in an exposed area of the
first energy beam on the resist film; a third step of irradiating
an entire surface of the resist film with the second energy beam,
generating the acid on the entire surface of the resist film, and
neutralizing the generated acid with the base generated in the
exposed area of the first energy beam on the resist film; a fourth
step of supplying metal alkoxide onto the resist film and forming a
metal oxide film on a surface of an unexposed area of the first
energy beam on the resist film; and a fifth step of forming a
resist pattern by dry-etching the resist film by using the metal
oxide film as a mask.
[0056] According to the fourth pattern forming method, in the
exposed area of the first energy beam on the resist film, since the
base generated through the pattern exposure using the first energy
beam is neutralized with the acid generated through the entire
surface exposure using the second energy beam, the metal oxide film
cannot be formed in the exposed area. On the other hand, in the
unexposed area of the first energy beam on the resist film, since
the acid is generated through the entire surface exposure using the
second energy beam, the metal oxide film can be formed owing to the
catalytic function of the acid by supplying the metal alkoxide.
Accordingly, through the dry etching of the resist film using the
metal oxide film as a mask, a positive type resist pattern can be
formed.
[0057] Furthermore, according to the fourth pattern forming method,
since the metal oxide film can be formed owing to the catalytic
function of the acid in the unexposed area of the first energy beam
on the resist film, the resultant metal oxide film can attain a
high density and sufficient strength.
[0058] In the fourth pattern forming method, the second group is
preferably a group for generating sulfonic acid. In this case,
since sulfonic acid is a strong acid, it is possible to form a
metal oxide film having a sufficient density in the unexposed area
of the first energy beam on the resist film owing to the strong
catalytic function of sulfonic acid. As a result, the selectivity
in the dry etching is high, and it is possible to form a more
fine-line positive type resist pattern having a satisfactory
shape.
[0059] In the third or fourth pattern forming method, the fourth
step preferably includes a step of allowing the unexposed area on
the resist film to adsorb water. In this case, since water is
diffused into a deep portion from the surface of the unexposed area
of the first energy beam on the resist film, the metal oxide film
formed in the unexposed area can attain a large thickness.
[0060] The copolymer used in the third or fourth pattern forming
method is preferably a binary copolymer represented by the
following general formula or a ternary or higher copolymer obtained
by further polymerizing the binary copolymer with another group:
7
[0061] wherein R.sub.9 indicates a hydrogen atom or an alkyl group;
R.sub.10 and R.sub.11 independently indicate a hydrogen atom, an
alkyl group, a phenyl group or an alkenyl group, or together
indicate a cyclic alkyl group, a cyclic alkenyl group, a cyclic
alkyl group having a phenyl group or a cyclic alkenyl group having
a phenyl group; R.sub.12 indicates a hydrogen atom or an alkyl
group; R.sub.13 and R.sub.14 independently indicate a hydrogen
atom, an alkyl group, a phenyl group or an alkenyl group, or
together indicate a cyclic alkyl group, a cyclic alkenyl group, a
cyclic alkyl group having a phenyl group or a cyclic alkenyl group
having a phenyl group; x satisfies a relationship of 0<x<1;
and y satisfies a relationship of 0<y <1.
[0062] When the copolymer represented by Chemical Formula 6 is used
in the third pattern forming method, since sulfonic acid generated
through the pattern exposure using the first energy beam is
neutralized with amine generated through the entire surface
exposure using the second energy beam, the metal oxide film cannot
be formed in the exposed area of the first energy beam on the
resist film. On the other hand, in the unexposed area of the first
energy beam on the resist film, since amine having a strong basic
property is generated through the entire surface exposure using the
second energy beam, the metal oxide film with a sufficient density
can be formed by supplying the metal alkoxide to the resist film.
Accordingly, the selectivity in the dry etching is very high, and
it is possible to form a more fine-line positive resist pattern
having a satisfactory shape.
[0063] When the copolymer represented by Chemical Formula 6 is used
in the fourth pattern forming method, since amine generated through
the pattern exposure using the first energy beam is neutralized
with sulfonic acid generated through the entire surface exposure
using the second energy beam, the metal oxide film cannot be formed
in the exposed area of the first energy beam on the resist film. On
the other hand, in the unexposed area of the first energy beam on
the resist film, since sulfonic acid having a strong acidic
property is generated through the entire surface exposure using the
second energy beam, the metal oxide film with a sufficient density
can be formed by supplying the metal alkoxide. Accordingly, the
selectivity in the dry etching is very high, and it is possible to
form a more fine-line positive type resist pattern having a
satisfactory shape.
BRIEF DESCRIPTION OF THE DRAWINGS
[0064] FIGS. 1(a) through 1(d) are sectional views for showing
procedures of a pattern forming method according to a first
embodiment of the invention;
[0065] FIGS. 2(a) through 2(d) are sectional views for showing
procedures of a pattern forming method according to a second
embodiment of the invention;
[0066] FIGS. 3(a) through 3(c) are sectional views for showing
procedures of a pattern forming method according to a third
embodiment of the invention;
[0067] FIGS. 4(a) and 4(b) are sectional views for showing other
procedures of the pattern forming method of the third embodiment;
and
[0068] FIGS. 5(a) through 5(d) are sectional views for showing
procedures of a conventional pattern forming method.
DETAILED DESCRIPTION OF THE INVENTION
Embodiment 1
[0069] FIGS. 1(a) through 1(d) are sectional views for showing
procedures of a pattern forming method of a first embodiment.
[0070] As a resist material, a copolymer represented by Chemical
Formula 7 dissolved in diglyme is used. 8
[0071] First, as is shown in FIG. 1(a), the resist material is
spin-coated on a semiconductor substrate 100 of silicon, and the
resultant semiconductor substrate is annealed at a temperature of
90.degree. C. for 90 seconds, thereby forming a resist film 101
with a thickness of 1 .mu.m. At this point, no peeling is observed,
and the resist film 101 has satisfactory adhesion. Then, by using a
mask 103, the substrate is irradiated with a KrF excimer laser 104,
i.e., an energy beam, thereby transferring a pattern of the mask
103 onto the resist film 101. In this manner,
O-acryloyl-acetophenone-oxime (AAPO) is dissolved to generate amine
on the surface of an exposed area 101a of the resist film 101. A
reaction caused through the exposure of the resist material is
shown as Chemical Formula 8. 9
[0072] An unexposed area 101b of the resist film 101 has a strong
acidic property owing to the function of a sulfonic acid group in
Chemical Formula 7. On the other hand, in the exposed area 101a of
the resist film 101, AAPO in Chemical Formula 7 is dissolved into
amine having a basic property, and the amine neutralizes the acidic
property resulting from the function of the sulfonic acid group. At
this point, since the unexposed area 101b has the strong acidic
property, water is more easily adsorbed in the unexposed area 101b
than in the exposed area 101a which has been neutralized. In other
words, since the unexposed area 101b includes the group having the
strong acidic property, a hydrogen bond with water is strengthened
in the unexposed area 101b, and hence water can be easily adsorbed.
In contrast, in the exposed area 101a, a hydrogen bond with water
is weakened by the neutralization, and water cannot be easily
adsorbed.
[0073] Next, as is shown in FIG. 1(b), the semiconductor substrate
100 is allowed to stand in air with a relative humidity of 95% at a
temperature of 30.degree. C. for 30 minutes, thereby supplying
water vapor 105 onto the surface of the resist film 101. In this
manner, the water vapor 105 is adsorbed by the surface of the
unexposed area 101b, which can easily adsorb water, and the
adsorbed water is diffused into a deep portion, for example, at a
depth of 100 nm from the surface of the unexposed area 101b. Since
the exposed area 101a has been neutralized, water is difficult to
be adsorbed. Thus, a water adsorbing layer 106 is selectively
formed in the unexposed area 101b.
[0074] Then, as is shown in FIG. 1(c), while retaining the
semiconductor substrate 100 in the air with the relative humidity
of 95% at a temperature of 30.degree. C., vapor 107 of
methyltriethoxysilane (MTEOS), i.e., metal alkoxide, is sprayed
onto the surface of the resist film 101 for 3 minutes, thereby
selectively forming an oxide film 108 on the surface of the
unexposed area 101b of the resist film 101. In this case, an acid
(H.sup.+) derived from sulfonic acid works as a catalyst in
hydrolysis and dehydration of MTEOS, so that the oxide film 108 can
be formed. Therefore, the oxide film 108 is formed merely a portion
where both H.sup.+ serving as the catalyst and water are
present.
[0075] According to the first embodiment, the oxide film is not
formed in the exposed area 101a of the resist film 101 because
sulfonic acid is neutralized by the generated amine and loses its
function as the catalyst and water cannot be easily adsorbed in the
exposed area 101a. On the other hand, the oxide film 108 is formed
in the unexposed area 101b of the resist film 101 because H.sup.+
serving as the catalyst is present and a sufficient amount of water
has been adsorbed in the unexposed area 101b.
[0076] Next, as is shown in FIG. 1(d), by using the oxide film 108
as a mask, the semiconductor substrate 100 is subjected to RIE
(reactive ion etching) using O.sub.2 plasma 109, thereby forming a
resist pattern 110. In this case, the RIE using O.sub.2 plasma is
effected by using a parallel plate reactive ion etching system
under conditions of a power of 900 W, a pressure of 0.7 Pa and a
flow rate of 40 SCCM.
[0077] In this embodiment, since the oxide film 108 is selectively
formed in the unexposed area 101b alone and the etching is effected
by using the oxide film 108, the positive type resist pattern 110
having a vertical section can be formed in the unexposed area
101b.
[0078] Furthermore, since the water vapor 105 is supplied to the
resist film 101 in the procedure shown in FIG. 1(b), water is
diffused into the deep portion from the surface of the unexposed
area 101b of the resist film 101, so that the oxide film 108 can be
shown toward the inside of the resist film 101. As a result, the
oxide film 108 can attain a large thickness.
[0079] In addition, since MTEOS is supplied to the resist film 101
in the air with the relative humidity of 95% in the procedure shown
in FIG. 1(c), equilibrium of water can be retained so that the
water having been adsorbed by the resist film 101 can be prevented
from evaporating and that water can be supplied in a sufficient
amount for the formation of the oxide film 108. As a result, the
resultant oxide film 108 can attain a thickness sufficiently large
for withstanding the RIE using O.sub.2 plasma.
[0080] After the supply of MTEOS, the resist film 101 can be
allowed to stand in vacuum so as to evaporate alcohol included in
the oxide film 108. Thus, the flow of the oxide film 108 can be
avoided.
[0081] In this manner, the resist film 101 of the resist material
including an acidic group is subjected to the pattern exposure in
this embodiment. In the exposed area 101a, a base is generated to
neutralize the acidic property of the exposed area 101a, and the
oxide film 108 is selectively formed in the unexposed area 101b
alone, so as to be used in etching the resist film 101.
Accordingly, it is possible to form the positive type fine-line
resist pattern 110 having a satisfactory shape.
[0082] Also, since water is forcedly adsorbed in the unexposed area
101b before forming the oxide film 108, the resultant oxide film
108 can attain a large thickness required for the dry development
by the RIE using O.sub.2 plasma.
[0083] In the resist material used in the first embodiment, the
copolymer represented by Chemical Formula 7 includes styrene
sulfonic acid as the acidic group. However, the acidic group is not
limited to styrene sulfonic acid but can be any group having a
strong acidic property and including a group represented by
Chemical Formula 9. 10
[0084] Furthermore, MTEOS is used as the metal alkoxide in this
embodiment, but MTEOS can be replaced with any other metal alkoxide
in a gas or liquid phase such as Si(OCH.sub.3
).sub.4(tetramethoxysilane),
Si(OC.sub.2H.sub.5).sub.4(tetraethoxysilane),
Ti(OC.sub.2H.sub.5).sub.4, Ge(OC.sub.2H.sub.5).sub.4,
Al(OC.sub.2H.sub.5).sub.3, and Zr(OC.sub.2H.sub.5).sub.3.
[0085] Also, the dry development is effected by the RIE using
O.sub.2 plasma in this embodiment, but ECR (electron cyclotron
resonance etching) using O.sub.2 plasma is adoptable instead.
[0086] Moreover, a light source for the exposure is the KrF excimer
laser in this embodiment, but an i-line, an ArF excimer laser, EB,
X-rays or the like can be used.
[0087] Furthermore, in the procedure for diffusing water in the
surface of the unexposed area 101b of the resist film 101 in this
embodiment, the semiconductor substrate 100 is allowed to stand in
the water vapor, but water in a liquid phase can be supplied to the
resist film 101 on the semiconductor substrate 100 instead.
However, water can be more rapidly diffused and the thickness of
the oxide film 108 can be more increased when the water is supplied
in a gas phase than in a liquid phased and hence, water is
preferably supplied in a gas phase.
Embodiment 2
[0088] FIGS. 2(a) through 2(d) are sectional views for showing
procedures of a pattern forming method of a second embodiment.
[0089] As a resist material, a copolymer represented by Chemical
Formula 10 dissolved in diglyme is used. 11
[0090] First, as is shown in FIG. 2(a), similarly to the first
embodiment, the resist material is spin-coated on a semiconductor
substrate 200 of silicon; and the semiconductor substrate 200 is
annealed at a temperature of 90.degree. C. for 90 seconds, thereby
forming a resist film 201 with a thickness of 1 .mu.m. At this
point, no peeling is observed, and the resultant resist film 201
has satisfactory adhesion. Then, by using a mask 203, the
semiconductor substrate 200 is irradiated with a KrF excimer laser
204, i.e., an energy beam, thereby transferring a pattern of the
mask 203 onto the resist film 201. In this manner, on the surface
of an exposed area 201a of the resist film 201,
1,2,3,4-tetrahydronaphthy- ridinenimino-p-styrene sulfonate (NISS)
is dissolved to generate sulfonic acid. A reaction caused through
the exposure of the resist material is shown as Chemical Formula
11. 12
[0091] An unexposed area 201b of the resist film 201 has a basic
property owing to the function of an amino group in Chemical
Formula 10. On the other hand, in the exposed area 201a of the
resist film 201, NISS in Chemical Formula 10 is dissolved into
sulfonic acid having a strong acidic property, so that the basic
property derived from the function of the amino group can be
neutralized. In this case, since the unexposed area 201b has the
strong basic property, water can be more easily adsorbed in the
unexposed area 201b than in the exposed area 201a having been
neutralized. Specifically, since the unexposed area 201b includes
the group having the strong basic property, a hydrogen bond with
water is strengthened, and water can be easily adsorbed. In
contrast, in the exposed area 201a, a hydrogen bond with water is
weakened by the neutralization, and water cannot be easily
adsorbed.
[0092] Next, as is shown in FIG. 2(b), the semiconductor substrate
200 is allowed to stand in air with a relative humidity of 95% at a
temperature of 30.degree. C. for 30 minutes, thereby supplying
water vapor 205 onto the surface of the resist film 201. In this
manner, the water vapor 205 is adsorbed by the surface of the
unexposed area 201b, which can easily adsorb water, and the
adsorbed water is diffused into a deep portion, for example, at a
depth of 100 nm from the surface of the unexposed area 201b of the
resist film 201. Since the exposed area 201a has been neutralized,
water cannot be easily adsorbed. Thus, a water adsorbing layer 206
is selectively formed in the unexposed area 201b.
[0093] Then, as is shown in FIG. 2(c), while retaining the
semiconductor substrate 200 in the air with the relative humidity
of 95% at a temperature of 30.degree. C., vapor 207 of MTEOS, i.e.,
metal alkoxide, is sprayed onto the surface of the resist film 201
for 3 minutes, thereby selectively forming an oxide film 208 on the
surface of the unexposed area 201b of the resist film 201. In this
case, the base derived from the amino group works as a catalyst in
the hydrolysis and dehydration of MTEOS, so that the oxide film 208
can be formed. Therefore, the oxide film 208 is formed merely in a
portion where both the base serving as the catalyst and water are
present.
[0094] According to the second embodiment, in the exposed area 201a
of the resist film 201, since the amino group is neutralized by
generated sulfonic acid and loses its function as the catalyst and
water cannot be easily adsorbed, the oxide film cannot be formed.
In contrast, in the unexposed area 201b of the resist film 201, the
base serving as the catalyst is present and a sufficient amount of
water has been adsorbed, the oxide film 208 can be formed.
[0095] Then, as is shown in FIG. 2(d), by using the oxide film 208
as a mask, the RIE using O.sub.2 plasma is effected, thereby
forming a resist pattern 210. The RIE using O.sub.2 plasma is
effected by using a parallel plate reactive ion etching system
under conditions of a power of 900 W, a pressure of 0.7 Pa and a
flow rate of 40 SCCM.
[0096] In this embodiment, since the oxide film 208 is selectively
formed in the unexposed area 201b alone to be used in the etching,
the positive type resist pattern 210 having a vertical section can
be formed in the unexposed area 201b.
[0097] Furthermore, since the water vapor 205 is supplied to the
resist film 201 in the procedure shown in FIG. 2(b), water is
diffused into the deep portion from the surface of the unexposed
area 201b of the resist film 201, so that the oxide film 208 can be
grown toward the inside of the resist film 201. As a result, the
oxide film 208 can attain a large thickness.
[0098] In addition, since MTEOS is supplied to the resist film 201
in the air with the relative humidity of 95% in the procedure shown
in FIG. 2(c), equilibrium of water can be retained so that the
water having been adsorbed by the resist film 201 can be prevented
from evaporating and that water can be supplied in a sufficient
amount for the formation of the oxide film 208. As a result, the
resultant oxide film 208 can attain a thickness sufficiently large
for withstanding the RIE using O.sub.2 plasma.
[0099] After the supply of MTEOS, the resist film 201 can be
allowed to stand in vacuum so as to evaporate alcohol included in
the oxide film 208. Thus, the flow of the oxide film 208 can be
avoided.
[0100] In this manner, the resist film 201 of the resist material
including a basic group is subjected to the pattern exposure in
this embodiment. In the exposed area 201a, a strong acid is
generated to neutralize the basic property of the exposed area
201a, and the oxide film 208 is selectively formed in the unexposed
area 201b alone, so as to be used in etching the resist film 201.
Accordingly, it is possible to form the positive type fine-line
resist pattern 210 having a satisfactory shape.
[0101] Also, since water is forcedly adsorbed in the unexposed area
201b before forming the oxide film 208, the resultant oxide film
208 can attain a large thickness required for the dry development
by the RIE using O.sub.2 plasma.
[0102] In the resist material used in the second embodiment, the
copolymer represented by Chemical Formula 10 includes the amono
group as the basic group. However, the basic group is not limited
to the amino group but can be any group having a basic
property.
[0103] Furthermore, MTEOS is used as the metal alkoxide in this
embodiment, but MTEOS can be replaced with any other metal alkoxide
in a gas or liquid phase such as
Si(OCH.sub.3).sub.4(tetramethoxysilane),
Si(OC.sub.2H.sub.5).sub.4(tetraethoxysilane),
Ti(OC.sub.2H.sub.5).sub.4, Ge(OC.sub.2H.sub.5).sub.4,
Al(OC.sub.2H.sub.5).sub.3, and Zr(OC.sub.2H.sub.5).sub.3.
[0104] Also, the dry development is effected by the RIE using
O.sub.2 plasma in this embodiment, but ECR (electron cyclotron
resonance etching) using O.sub.2 plasma is adoptable instead.
[0105] Moreover, a light source for the exposure is the KrF excimer
laser in this embodiment, but an i-line, an ArF excimer laser, ES,
X-rays or the like can be used.
[0106] Furthermore, in the procedure for diffusing water in the
surface of the unexposed area 201b of the resist film 201 in this
embodiment, the semiconductor substrate 200 is allowed to stand in
the water vapor, but water in a liquid phase can be supplied to the
resist film 201 on the semiconductor substrate 200 instead.
However, water can be more rapidly diffused and the thickness of
the oxide film 208 can be more increased when the water is supplied
in a gas phase than in a liquid phase, and hence, water is
preferably supplied in a gas phase.
Embodiment 3
[0107] FIGS. 3(a) through 3(c), 4(a) and 4(b) are sectional views
for showing procedures of a pattern forming method of a third
embodiment.
[0108] As a resist material, a copolymer represented by Chemical
Formula 12 dissolved in diglyme is used. A sulfonic acid generating
group selectively generates sulfonic acid through irradiation with
an ArF excimer laser, and an amine generating group selectively
generates amine through irradiation with an i-line. 13
[0109] First, as is shown in FIG. 3(a), similarly to the first
embodiment, the resist material is spin-coated on a semiconductor
substrate 300 of silicon, and the semiconductor substrate is
annealed at a temperature of 90.degree. C. for 90 seconds, thereby
forming a resist film 301 with a thickness of 1 .mu.m. At this
point, no peeling is observed, and the resultant resist film 301
has satisfactory adhesion. Then, by using a mask 303, the
semiconductor substrate 300 is irradiated with an ArF excimer laser
304, i.e., a first energy beam, thereby transferring a pattern of
the mask 303 onto the resist film 301. In this manner, on the
surface of an exposed area 301a of the resist film 301, the
sulfonic acid generating group is dissolved into sulfonic acid, and
the exposed area 301a attains a strong acidic property. A reaction
caused through the exposure of the resist material is shown as
Chemical Formula 13. 14
[0110] Next, as is shown in FIG. 3(b), the entire surface of the
resist film 301 is irradiated with an i-line 305, i.e., a second
energy beam. In this manner, in the exposed area 301a where the
pattern has been transferred through the irradiation with the ArF
excimer laser 304, amine having a basic property is generated
through the entire surface exposure with the i-line 305 as is shown
in a reaction formula of Chemical Formula 14. Thus, the acidic
property of the exposed area 301a is neutralized. 15
[0111] On the other hand, in an unexposed area 301b where the
pattern exposure has not been effected through the irradiation with
ArF excimer laser 304, amine is generated on the surface of the
resist film 301 through the entire surface exposure with the i-line
305 as is shown in a reaction formula of Chemical Formula 15, so
that the unexposed area 301b attains a basic property. At this
point, since the unexposed area 301b has a strong basic property,
water can be more easily adsorbed than in the exposed area 301a
having been neutralized. 16
[0112] Then, as is shown in FIG. 3(c), the semiconductor substrate
300 is allowed to stand in air with a relative humidity of 95% at a
temperature of 30.degree. C. for 30 minutes, thereby supplying
water vapor 307 onto the surface of the resist film 301. In this
manner, the water vapor 307 is adsorbed by the surface of the
unexposed area 301b which can easily adsorb water, and the adsorbed
water is diffused into a deep portion, for example, at a depth of
100 nm from the surface of the unexposed area 301b of the resist
film 301. Since the exposed area 301a is neutralized, water cannot
be easily adsorbed. Thus, a water adsorbing layer 308 is
selectively formed in the unexposed area 301b.
[0113] Next, as is shown in FIG. 4(a), while retaining the
semiconductor substrate 300 in the air with the relative humidity
of 95% at a temperature of 30.degree. C., vapor 309 of MTEOS, i.e.,
metal alkoxide, is sprayed onto the surface of the resist film 301
for 3 minutes, thereby selectively forming an oxide film 310 on the
surface of the unexposed area 301b. In this case, the base, the
amino group, works as a catalyst in the hydrolysis and dehydration
of MTEOS, so that the oxide film 310 can be formed. Therefore, the
oxide film 310 is formed merely in a portion where both the base
working as the catalyst and water are present.
[0114] According to the third embodiment, in the exposed area 301a
of the resist film 301, since amine is neutralized by generated
sulfonic acid and loses its function as the catalyst and water
cannot be easily adsorbed, the oxide film cannot be formed. On the
other hand, in the unexposed area 301b of the resist film 301,
since the base serving as the catalyst is present and a sufficient
amount of water has been adsorbed, the oxide film 310 can be
formed.
[0115] Then, as is shown in FIG. 4(b), by using the oxide film 310
as a mask, the RIE using O.sub.2 plasma 311 is effected, thereby
forming a resist pattern 312. The RIE using O.sub.2 plasma is
effected by using a parallel plate reactive ion etching system
under conditions of a power of 900 W, a pressure of 0.7 Pa and a
flow rate of 40 SCCM.
[0116] In this embodiment, since the oxide film 310 is selectively
formed in the unexposed area 301b alone to be used in the etching,
the positive type resist pattern 312 having a vertical section can
be formed in the unexposed area 301b.
[0117] Furthermore, since the water vapor 307 is supplied to the
resist film 301 in the procedure shown in FIG. 3(c), water is
diffused into the deep portion from the surface of the unexposed
area 301b of the resist film 301, so that the oxide film 310 can be
grown toward the inside of the resist film 301. As a result, the
oxide film 310 can attain a large thickness. In particular, since
the base is generated merely on the surface of the resist film 301,
the thickness of the water adsorbing layer 308 can be limited to a
depth where the base is generated. As a result, water can be
prevented from invading a portion below the exposed area 301a.
[0118] In addition, since MTEOS is supplied to the resist film 301
in the air with the relative humidity of 95% in the procedure shown
in FIG. 4(a), equilibrium of water can be retained so that the
water having been adsorbed by the resist film 301 can be prevented
from evaporating and that water can be supplied in a sufficient
amount for the formation of the oxide film 310. As a result, the
resultant oxide film 310 can attain a thickness sufficiently large
for withstanding the RIE using O.sub.2 plasma.
[0119] After the supply of MTEOS, the resist film 301 can be
allowed to stand in vacuum so as to evaporate alcohol included in
the oxide film 310. Thus, the flow of the oxide film 310 can be
avoided.
[0120] In this manner, according to the method of this embodiment,
after generating a strong acid in the exposed area 301a through the
pattern exposure using the first energy beam, a base is generated
through the entire surface exposure using the second energy beam
having a different energy band from the first energy beam. Thus,
the exposed area 301a of the pattern exposure is neutralized, while
the unexposed area 301b of the pattern exposure attains the basic
property. Therefore, the oxide film 310 can be selectively formed
in the unexposed area 301b of the pattern exposure, and the resist
film 301 is etched by using the oxide film 310. As a result, it is
possible to form the positive type fine-line resist pattern 312
having a satisfactory shape.
[0121] Also, since water is forcedly adsorbed in the unexposed area
301b before forming the oxide film 310, the resultant oxide film
310 can attain a large thickness required for the dry development
by the RIE using O.sub.2 plasma.
[0122] Furthermore, MTEOS is used as the metal alkoxide in this
embodiment, but MTEOS can be replaced with any other metal alkoxide
in a gas or liquid phase such as
Si(OCH.sub.3).sub.4(tetramethoxysilane),
Si(OC.sub.2H.sub.5).sub.4(tetraethoxysilane),
Ti(OC.sub.2H.sub.5).sub.4, Ge(OC.sub.2H.sub.5).sub.4,
Al(OC.sub.2H.sub.5).sub.3, and Zr(OC.sub.2H.sub.5).sub.3.
[0123] Also, the dry development is effected by the RIE using
O.sub.2 plasma in this embodiment, but ECR (electron cyclotron
resonance etching) using O.sub.2 plasma is adoptable instead.
[0124] Furthermore, in the procedure for diffusing water in the
surface of the unexposed area 301b of the resist film 301 in this
embodiment, the semiconductor substrate 300 is allowed to stand in
the water vapor, but water in a liquid phase can be supplied to the
resist film 301 on the semiconductor substrate 300 instead.
However, water can be more rapidly diffused and the thickness of
the oxide film 310 can be more increased when the water is supplied
in a gas phase than in a liquid phase, and hence, water is
preferably supplied in a gas phase.
[0125] Alternatively, the effects to form a positive type fine-line
resist pattern having a satisfactory shape of the third embodiment
can also be attained as follows: A copolymer which can generate a
base through irradiation with a first energy beam and an acid
through irradiation with a second energy beam is used as a resist
material. Through the irradiation with the first energy beam, a
desired pattern is exposed so that the base is selectively
generated in an exposed area. Then, through the irradiation of the
entire surface with the second energy beam, the acid is generated
on the entire surface of the resist film. Thus, the exposed area of
the pattern exposure using the first energy beam is neutralized.
Water vapor is then supplied to an unexposed area of the pattern
exposure so that water can be adsorbed by the unexposed area. Then,
both water vapor and alkoxysilane are supplied to the unexposed
area, thereby forming an oxide film in the unexposed area. By using
the oxide film, the resist film is etched, thereby forming a resist
pattern.
[0126] In the first through third embodiments, the copolymers
represented by Chemical Formulas 7, 10 and 12 are used as the
resist materials. However, for example, a group for generating
sulfonic acid represented by any of Chemical Formulas 16 through 21
can be used as the sulfonic acid generating group. Also, the
sulfonic acid generating group can be appropriately replaced with a
group having a strong acidic property. 17
[0127] Furthermore, as the amine generating group, for example, a
group for generating amine represented by any of Chemical Formulas
22 through 27 can be used, and the amine generating group can be
appropriately replaced with a group having a basic property. 18
[0128] Moreover, the ArF excimer laser is used as a light source
for the pattern exposure using the first energy beam, but the ArF
excimer laser can be replaced with an i-line, a KrF excimer laser,
EB, X-rays or the like. The i-line is used as a light source for
the entire surface exposure using the second energy beam, but the
i-line can be replaced with any other appropriate light source
having a different energy band from that of the first energy beam.
In this case, in accordance with the kinds of the first and second
energy beams to be used, the sulfonic acid generating group or the
group having an acidic property, and the amine generating group or
the group having a basic property can be appropriately
selected.
[0129] Furthermore, in the first through third embodiments, the
copolymers including the sulfonic acid generating group or the
amine generating group are used, but the copolymer can be replaced
with another ternary or higher polymer obtained by further
polymerizing any of the aforementioned binary polymers with a group
represented by Chemical Formula 28 or 29. 19
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