Chemically amplified resist material and pattern formation method using the same

Abstract

In the pattern formation method, a resist film is formed on a substrate by using a chemically amplified resist material including fumaric acid substituted by an acid labile group released by an acid; an alkali-soluble polymer soluble in an alkaline solution; and a photo-acid generator for generating an acid through irradiation with light. Subsequently, pattern exposure is carried out by selectively irradiating the resist film with exposing light, and a resist pattern is formed by developing the resist film after the pattern exposure.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A, 1B, 1C and 1D are cross-sectional views for showing procedures in a pattern formation method using a chemically amplified resist material according to Embodiment 1 of the invention;

FIGS. 2A, 2B, 2C and 2D are cross-sectional views for showing procedures in a pattern formation method using a chemically amplified resist material according to Embodiment 2 of the invention;

FIGS. 3A, 3B, 3C and 3D are cross-sectional views for showing procedures in a pattern formation method using a chemically amplified resist material according to Embodiment 3 of the invention;

FIGS. 4A, 4B, 4C and 4D are cross-sectional views for showing procedures in a pattern formation method using a chemically amplified resist material according to Embodiment 4 of the invention; and

FIGS. 5A, 5B, 5C and 5D are cross-sectional views for showing procedures in a conventional pattern formation method.

DETAILED DESCRIPTION OF THE INVENTION

Embodiment 1

A chemically amplified resist material and a pattern formation method using the same according to Embodiment 1 of the invention will now be described with reference to FIGS. 1A through 1D.

First, a positive chemically amplified resist material having, for example, the following composition is prepared:

Base polymer: poly((methacrylic acid)	2	g
(30 mol %)-(γ-butyrolactone
methacrylate) (50 mol %)-(2-hydroxyadamantyl
methacrylate) (20 mol %))
Dissolution inhibitor: di-t-butyl fumarate	0.8	g
Photo-acid generator: triphenylsulfonium nonafluorobutane	0.06	g
sulfonate
Quencher: triethanolamine	0.001	g
Solvent: propylene glycol monomethyl ether acetate	20	g

Next, as shown in FIG. 1A, the aforementioned chemically amplified resist material is applied on a substrate 101 so as to form a resist film 102 with a thickness of 0.35 μm.

Then, as shown in FIG. 1B, pattern exposure is carried out by irradiating the resist film 102 with exposing light 104 of ArF excimer laser with NA of 0.68 through a mask 103.

After the pattern exposure, as shown in FIG. 1C, the resist film 102 is baked with a hot plate at a temperature of 105° C. for 60 seconds. Thereafter, the resultant resist film 102 is developed with a 0.26 N tetramethylammonium hydroxide developer. Thus, a resist pattern 102a made of an unexposed portion of the resist film 102, having a line width of 0.09 μm and having high resolution is formed as shown in FIG. 1D.

In this manner, according to Embodiment 1, the chemically amplified resist material includes the dissolution inhibitor of the di-t-butyl fumarate, that is, fumaric acid substituted by an acid labile group of a t-butyl group. Therefore, the dissolution is accelerated in an exposed portion of the resist film 102 because the t-butyl group is released by an acid generated from the photo-acid generator therein, and on the other hand, the dissolution rate is lowered in an unexposed portion because no t-butyl group is released therein. As a result, the contrast is improved in the resist film 102 in the development, so that the resist pattern 102a can be formed in a good shape.

Embodiment 2

A chemically amplified resist material and a pattern formation method using the same according to Embodiment 2 of the invention will now be described with reference to FIGS. 2A through 2D.

First, a positive chemically amplified resist material having, for example, the following composition is prepared:

Base polymer: poly((2-methyl-2-adamantyl methacrylate)	2	g
(50 mol %)-(γ-butyrolactone methacrylate) (40 mol %)-(2-
hydroxyadamantyl methacrylate) (10 mol %))
Dissolution inhibitor: di-t-butyl fumarate	0.5	g
Photo-acid generator: triphenylsulfonium	0.06	g
nonafluorobutane sulfonate
Quencher: triethanolamine	0.001	g
Solvent: propylene glycol monomethyl ether acetate	20	g

Next, as shown in FIG. 2A, the aforementioned chemically amplified resist material is applied on a substrate 201 so as to form a resist film 202 with a thickness of 0.35 μm.

Then, as shown in FIG. 2B, pattern exposure is carried out by irradiating the resist film 202 with exposing light 204 of ArF excimer laser with NA of 0.68 through a mask 203.

After the pattern exposure, as shown in FIG. 2C, the resist film 202 is baked with a hot plate at a temperature of 105° C. for 60 seconds. Thereafter, the resultant resist film 202 is developed with a 0.26 N tetramethylammonium hydroxide developer. Thus, a resist pattern 202a made of an unexposed portion of the resist film 202, having a line width of 0.09 μm and having high resolution is formed as shown in FIG. 2D.

In this manner, according to Embodiment 2, the chemically amplified resist material includes the dissolution inhibitor of the di-t-butyl fumarate, that is, fumaric acid substituted by a first acid labile group of a t-butyl group. Therefore, the dissolution is accelerated in an exposed portion of the resist film 202 because the t-butyl group is released by an acid generated from the photo-acid generator therein, and on the other hand, the dissolution rate is lowered in an unexposed portion because no t-butyl group is released therein. As a result, the contrast is improved in the resist film 202 in the development, so that the resist pattern 202a can be formed in a good shape.

In addition, the base polymer is substituted by a second acid labile group, that is, a 2-methyl-2-adamantyl group in this embodiment, and hence, the dissolution inhibiting effect attained in the unexposed portion can be further increased. Specifically, the dissolution rate attained in the unexposed portion is further lowered, so as to further improve the contrast.

Embodiment 3

A chemically amplified resist material and a pattern formation method using the same according to Embodiment 3 of the invention will now be described with reference to FIGS. 3A through 3D.

First, a positive chemically amplified resist material having, for example, the following composition is prepared:

Base polymer: poly((methacrylic acid) (30 mol %)-	2	g
(γ-butyrolactone methacrylate) (50 mol %)-
(2-hydroxyadamantyl methacrylate) (20 mol %))
Dissolution inhibitor: di-adamantyloxymethyl fumarate	0.6	g
Photo-acid generator: triphenylsulfonium	0.06	g
trifluoromethane sulfonate
Quencher: triethanolamine	0.001	g
Solvent: propylene glycol monomethyl ether acetate	20	g

Next, as shown in FIG. 3A, the aforementioned chemically amplified resist material is applied on a substrate 301 so as to form a resist film 302 with a thickness of 0.35 μm.

Then, as shown in FIG. 3B, an immersion liquid 303 of water is provided between the resist film 302 and a projection lens 305. In this state, pattern exposure is carried out by irradiating the resist film 302 with exposing light 304 of ArF excimer laser with NA of 0.68 through a mask not shown.

After the pattern exposure, as shown in FIG. 3C, the resist film 302 is baked with a hot plate at a temperature of 115° C. for 60 seconds. Thereafter, the resultant resist film 302 is developed with a 0.26 N tetramethylammonium hydroxide developer. Thus, a resist pattern 302a made of an unexposed portion of the resist film 302, having a line width of 0.09 μm and having high resolution is formed as shown in FIG. 3D.

In this manner, according to Embodiment 3, the chemically amplified resist material includes the dissolution inhibitor of the di-adamantyloxymethyl fumarate, that is, fumaric acid substituted by an acid labile group of an adamantyloxymethyl group. Therefore, the dissolution is accelerated in an exposed portion of the resist film 302 because the adamantyloxymethyl group is released by an acid generated from the photo-acid generator therein, and on the other hand, the dissolution rate is lowered in an unexposed portion because no adamantyloxymethyl group is released therein. As a result, the contrast is improved in the resist film 302 in the development, so that the resist pattern 302a can be formed in a good shape.

Embodiment 4

A chemically amplified resist material and a pattern formation method using the same according to Embodiment 4 of the invention will now be described with reference to FIGS. 4A through 4D.

First, a positive chemically amplified resist material having, for example, the following composition is prepared:

Base polymer: poly((2-methyl-2-adamantyl	2	g
methacrylate) (50 mol %)-(γ-butyrolactone methacrylate)
(40 mol %)-(2-hydroxyadamantyl methacrylate)
(10 mol %))
Dissolution inhibitor: di-adamantyloxymethyl fumarate	0.4	g
Photo-acid generator: triphenylsulfonium trifluoromethane	0.06	g
sulfonate
Quencher: triethanolamine	0.001	g
Solvent: propylene glycol monomethyl ether acetate	20	g

Next, as shown in FIG. 4A, the aforementioned chemically amplified resist material is applied on a substrate 401 so as to form a resist film 402 with a thickness of 0.35 μm.

Then, as shown in FIG. 4B, an immersion liquid 403 of water is provided between the resist film 402 and a projection lens 405. In this state, pattern exposure is carried out by irradiating the resist film 402 with exposing light 404 of ArF excimer laser with NA of 0.68 through a mask not shown.

After the pattern exposure, as shown in FIG. 4C, the resist film 402 is baked with a hot plate at a temperature of 115° C. for 60 seconds. Thereafter, the resultant resist film 402 is developed with a 0.26 N tetramethylammonium hydroxide developer. Thus, a resist pattern 402a made of an unexposed portion of the resist film 402, having a line width of 0.09 μm and having high resolution is formed as shown in FIG. 4D.

In this manner, according to Embodiment 4, the chemically amplified resist material includes the dissolution inhibitor of the di-adamantyloxymethyl fumarate, that is, fumaric acid substituted by a first acid labile group of an adamantyloxymethyl group. Therefore, the dissolution is accelerated in an exposed portion of the resist film 402 because the adamantyloxymethyl group is released by an acid generated from the photo-acid generator therein, and on the other hand, the dissolution rate is lowered in an unexposed portion because no adamantyloxymethyl group is released therein. As a result, the contrast is improved in the resist film 402 in the development, so that the resist pattern 402a can be formed in a good shape.

In addition, the base polymer is substituted by a second acid labile group, that is, a 2-methyl-2-adamantyl group in this embodiment, and hence, the dissolution inhibiting effect attained in the unexposed portion can be further increased. Specifically, the dissolution rate attained in the unexposed portion is further lowered, so as to further improve the contrast.

In each of Embodiments 1 through 4, the acid labile group may be a t-butyloxycarbonyl group, a methoxymethyl group or an ethoxyethyl group instead of a t-butyl group, a 2-methyl-2-adamantyl group or an adamantyloxymethyl group.

In each of Embodiments 1 through 4, the base polymer may be polyacrylic acid, polymethacrylic acid, polynorbornene methyl carboxylic acid, polynorbornene carboxylic acid, polynorbornene methyl hexafluoroisopropyl alcohol, polynorbornene hexafluoroisopropyl alcohol or polyvinyl phenol.

Furthermore, in each of Embodiments 1 through 4, the photo-acid generator may be 1,3-diphenyl diazodisulfone instead of triphenylsulfonium nonafluorobutane sulfonate or triphenylsulfonium trifluoromethane sulfonate.

Moreover, although the immersion liquid 303 or 403 is water in each of Embodiments 3 and 4, an acidic solution such as a cesium sulfate (Cs₂SO₄) aqueous solution or a phosphoric acid (H₃PO₄) aqueous solution may be used instead of the water. The concentration of the acidic aqueous solution is preferably 50 wt % or less, which does not limit the invention.

Although the exposing light is ArF excimer laser in each of Embodiments 1 through 4, the exposing light may be KrF excimer laser, Xe₂ laser, F₂ laser, KrAr laser or Ar₂ laser instead.

Also, in each of Embodiments 1 and 2, the exposing light may be extreme ultraviolet (EUV) or electron beam (EB).

As described so far, according to the chemically amplified resist material and the pattern formation method using the same of this invention, a resist pattern with high resolution can be formed in a good shape with exposing light of a 300 nm or shorter wavelength. Therefore, the invention is useful for a chemically amplified resist material suitably used in fine pattern processing for semiconductor devices and a pattern formation method using the same.

Claims

1. A chemically amplified resist material comprising: fumaric acid substituted by an acid labile group released by an acid;an alkali-soluble polymer soluble in an alkaline solution; anda photo-acid generator for generating an acid through irradiation with light.

2. The chemically amplified resist material of claim 1, wherein said acid labile group is a t-butyl group, a t-butyloxycarbonyl group, a methoxymethyl group, an adamantyloxymethyl group, an ethoxyethyl group or a 2-methyl-2-adamantyl group.

3. The chemically amplified resist material of claim 1, wherein said alkali-soluble polymer is polyacrylic acid, polymethacrylic acid, polynorbornene methyl carboxylic acid, polynorbornene carboxylic acid, polynorbornene methyl hexafluoroisopropyl alcohol, polynorbornene hexafluoroisopropyl alcohol or polyvinyl phenol.

4. The chemically amplified resist material of claim 1, wherein said photo-acid generator is triphenylsulfonium nonafluorobutane sulfonate, triphenylsulfonium trifluoromethane sulfonate or 1,3-diphenyl diazodisulfone.

5. A chemically amplified resist material comprising: fumaric acid substituted by a first acid labile group released by an acid;a polymer in which an alkali-soluble polymer soluble in an alkaline solution is substituted by a second acid labile group; anda photo-acid generator for generating an acid through irradiation with light.

6. The chemically amplified resist material of claim 5, wherein said first acid labile group is a t-butyl group, a t-butyloxycarbonyl group, a methoxymethyl group, an adamantyloxymethyl group, an ethoxyethyl group or a 2-methyl-2-adamantyl group.

7. The chemically amplified resist material of claim 5, wherein said second acid labile group is a t-butyl group, a t-butyloxycarbonyl group, a methoxymethyl group, an adamantyloxymethyl group, an ethoxyethyl group or a 2-methyl-2-adamantyl group.

8. The chemically amplified resist material of claim 5, wherein said alkali-soluble polymer is polyacrylic acid, polymethacrylic acid, polynorbornene methyl carboxylic acid, polynorbornene carboxylic acid, polynorbornene methyl hexafluoroisopropyl alcohol, polynorbornene hexafluoroisopropyl alcohol or polyvinyl phenol.

9. The chemically amplified resist material of claim 5, wherein said photo-acid generator is triphenylsulfonium nonafluorobutane sulfonate, triphenylsulfonium trifluoromethane sulfonate or 1,3-diphenyl diazodisulfone.

10. A pattern formation method comprising the steps of: forming, on a substrate, a resist film by using a chemically amplified resist material including fumaric acid substituted by a first acid labile group released by an acid, an alkali-soluble polymer soluble in an alkaline solution, and a photo-acid generator for generating an acid through irradiation with light;performing pattern exposure by selectively irradiating said resist film with exposing light; andforming a resist pattern by developing said resist film after the pattern exposure.

11. The pattern formation method of claim 10, wherein said alkali-soluble polymer is substituted by a second acid labile group released by an acid.

12. The pattern formation method of claim 10, wherein said first acid labile group is a t-butyl group, a t-butyloxycarbonyl group, a methoxymethyl group, an adamantyloxymethyl group, an ethoxyethyl group or a 2-methyl-2-adamantyl group.

13. The pattern formation method of claim 10, wherein said alkali-soluble polymer is polyacrylic acid, polymethacrylic acid, polynorbornene methyl carboxylic acid, polynorbornene carboxylic acid, polynorbornene methyl hexafluoroisopropyl alcohol, polynorbornene hexafluoroisopropyl alcohol or polyvinyl phenol.

14. The pattern formation method of claim 10, wherein said photo-acid generator is triphenylsulfonium nonafluorobutane sulfonate, triphenylsulfonium trifluoromethane sulfonate or 1,3-diphenyl diazodisulfone.

15. The pattern formation method of claim 10, wherein said exposing light is extreme ultraviolet (EUV) or electron beam (EB).

16. The pattern formation method of claim 10, wherein said exposing light is ArF excimer laser, KrF excimer laser, Xe2 laser, F2 laser, KrAr laser or Ar2 laser.

17. A pattern formation method comprising the steps of: forming, on a substrate, a resist film by using a chemically amplified resist material including fumaric acid substituted by a first acid labile group released by an acid, an alkali-soluble polymer soluble in an alkaline solution, and a photo-acid generator for generating an acid through irradiation with light;performing pattern exposure by selectively irradiating said resist film with exposing light with a liquid provided on said resist film; andforming a resist pattern by developing said resist film after the pattern exposure.

18. The pattern formation method of claim 17, wherein said alkali-soluble polymer is substituted by a second acid labile group released by an acid.

19. The pattern formation method of claim 18, wherein said second acid labile group is a t-butyl group, a t-butyloxycarbonyl group, a methoxymethyl group, an adamantyloxymethyl group, an ethoxyethyl group or a 2-methyl-2-adamantyl group.

20. The pattern formation method of claim 17, wherein said first acid labile group is a t-butyl group, a t-butyloxycarbonyl group, a methoxymethyl group, an adamantyloxymethyl group, an ethoxyethyl group or a 2-methyl-2-adamantyl group.

21. The pattern formation method of claim 17, wherein said alkali-soluble polymer is polyacrylic acid, polymethacrylic acid, polynorbornene methyl carboxylic acid, polynorbornene carboxylic acid, polynorbornene methyl hexafluoroisopropyl alcohol, polynorbornene hexafluoroisopropyl alcohol or polyvinyl phenol.

22. The pattern formation method of claim 17, wherein said photo-acid generator is triphenylsulfonium nonafluorobutane sulfonate, triphenylsulfonium trifluoromethane sulfonate or 1,3-diphenyl diazodisulfone.

23. The pattern formation method of claim 17, wherein said liquid is water.

24. The pattern formation method of claim 17, wherein said liquid is an acidic solution.

25. The pattern formation method of claim 24, wherein said acidic solution is a cesium sulfate aqueous solution or a phosphoric acid aqueous solution.

26. The pattern formation method of claim 17, wherein said exposing light is ArF excimer laser, KrF excimer laser, Xe2 laser, F2 laser, KrAr laser or Ar2 laser.