JP2008158308A - Pattern forming material and pattern forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the resolution of a resist pattern in a multilayer resist process. <P>SOLUTION: An underlay film 102 is formed on a substrate 101 and heated, the underlay film comprising a pattern forming material containing a polymer prepared by polymerization of cycloolefin having a crosslinking group, and a heat-acid generator generating an acid by heat. Then intermediate film 103 containing silicon is formed on the underlay film 102, and an upper film 104 comprising a resist is formed thereon. The upper film 104 is exposed to an exposure light 106, and the exposed upper film 104 is developed to form a first pattern 104a from the upper film 104. The intermediate film 103 is etched, by using the first pattern 104a a mask to form a second pattern 103a from the intermediate film 103. Furthermore, the first pattern 104a and the second pattern 103a are used as a mask to form a third pattern 102a, that is superior in the profile is formed from the lower film 102. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a pattern forming material suitable for a fine processing technique of a semiconductor device and a pattern forming method using the same.

  Along with the large integration of semiconductor integrated circuits and downsizing of semiconductor elements, acceleration of development of lithography technology is desired. At present, as exposure light, pattern formation is performed by photolithography using a mercury lamp, a KrF excimer laser, an ArF excimer laser or the like as a light source. Furthermore, recently, application of an ArF light source has been attempted in immersion lithography. Under such circumstances, it is important to extend the life of lithography using an ArF excimer laser, and development of resists used for lithography is being promoted.

  In order to perform lithography using an ArF excimer laser, there is a method of improving the resolution by changing the composition of the polymer contained in the resist material (see, for example, Non-Patent Document 1). However, it cannot be said that the resolution and shape of the pattern are sufficiently improved by changing the composition of the polymer contained in the normal resist material.

  Therefore, in recent years, measures have been taken to use a multilayer resist process in which a resist material is thinned and a material different from the resist material is laminated on the resist film. According to the multilayer resist process, in principle, the resolution and shape of the pattern are improved by the thin resist material. For this reason, a favorable pattern is formed by transferring the formed pattern to a multilayer film.

  7A to 7D, FIG. 8A to FIG. 8C, FIG. 9A, and FIG. 9B for pattern forming methods using conventional pattern forming materials. Will be described with reference to FIG.

  First, an underlayer film forming material having the following composition is prepared.

Polyvinylphenol (base polymer) ... 2g
Tris-1,3,5 (N-dihydroxymethyl) melamine (crosslinking agent) ……………… 0.1g
Triphenylsulfonium trifluoromethanesulfonic acid (thermal acid generator) ……………………………………………………………………………………………… ……… 0.06g
Propylene glycol monomethyl ether acetate (solvent) ……………… 20g
Next, as shown in FIG. 7A, the lower film forming material is applied onto the substrate 1 to form the lower film 2 having a thickness of 0.35 μm.

  Next, as shown in FIG. 7B, the lower layer film 2 is heated at a temperature of 200 ° C. for 90 seconds to crosslink the lower layer film 2.

  Next, as shown in FIG. 7 (c), an intermediate film 3 made of an intermediate film forming material (SHB-A759 manufactured by Shin-Etsu Chemical Co., Ltd.) having a thickness of 80 nm is formed on the crosslinked lower film 2. To do.

  Next, as shown in FIG. 7D, the intermediate layer film 3 is heated at a temperature of 120 ° C. for 120 seconds.

  Next, as shown in FIG. 8A, an upper film 4 made of a resist material (PAR-855 manufactured by Sumitomo Chemical Co., Ltd.) having a film thickness of 100 nm is formed on the heated intermediate film 3. Thereafter, pattern exposure is performed by irradiating the upper film 4 with exposure light 6 made of an ArF excimer laser having an NA (numerical aperture) of 0.85 through a mask 7.

  Next, as shown in FIG. 8B, the upper layer film 4 that has been subjected to pattern exposure is heated at a temperature of 105 ° C. for 60 seconds, and then developed with an alkali developer. As shown in c), the first pattern 4 a is formed from the upper layer film 4.

  Next, as shown in FIG. 9A, the middle layer film 3 is etched using the first pattern 4 a as a mask to form the second pattern 3 a from the middle layer film 3.

Next, as shown in FIG. 9B, by etching the lower layer film 2 using the first pattern 4a and the second pattern 3a as a mask, a first film having a line width of, for example, 90 nm is formed from the lower layer film 2. Three patterns 2a are formed.
SW Yoon et al., “Influence of resin properties to resist performance at ArF lithography”, Proc. SPIE, Vol.5376, p.583 (2004)

  However, as shown in FIG. 9B, in the pattern forming method using the conventional pattern forming material, the shape of the obtained third pattern 2a becomes defective.

  As a result of various studies on the multilayer resist process, the inventors of the present application have found that a pattern defect occurs in the lower layer film 2 when the second pattern 3a made of the intermediate layer film 3 is transferred to the lower layer film 2, and the pattern The defect is caused by insufficient etching resistance of the lower layer film 2, and the reason why the etching resistance is insufficient is caused by insufficient crosslinking reaction by the crosslinking agent contained in the lower layer film forming material. I found out. In other words, conventionally, the cross-linking agent is added to the material for forming the lower layer film to increase the cross-linking in the lower layer film. It does n’t happen enough.

  In view of the above, an object of the present invention is to improve the resolution of a resist pattern in a multilayer resist process.

  As described above, the inventors of the present invention have found that, in the multilayer resist process in lithography, the conventional underlayer film has insufficient crosslinking reaction, so that the etching resistance is not sufficient, and as a result, the resist pattern is deformed. It was.

  Based on the above, the present inventors examined a pattern forming material having sufficiently high etching resistance, and as a result, a pattern forming material comprising a polymer obtained by polymerizing a cycloolefin having a crosslinkable group and a thermal acid generator, or Acquired the knowledge that the use of a material for forming an underlayer film made of a polymer obtained by polymerizing a cycloolefin having a crosslinkable group and a thermal acid generator unit improves the resolution of the resist pattern in a multilayer resist process in lithography. Yes.

  A polymer obtained by polymerizing a cycloolefin having a crosslinkable group has a high carbon density at the time of crosslinking, a low hygroscopicity, a high glass transition temperature (Tg), and a high effect of improving etching resistance. These are inherent properties of cycloolefins, and are the effects increased by cross-linking through the cross-linkable group in the polymer.

  Note that, as in the prior art, simply adding a crosslinking agent in the lower layer material does not increase the degree of crosslinking because the degree of freedom of the crosslinking agent is large. Further, even if a crosslinkable group is bonded to a polymer obtained by polymerizing vinyl phenol used as a normal lower layer material, the degree of crosslinking does not increase because the degree of freedom of the vinyl group is large.

  Further, although there is a positive resist containing a polymer obtained by polymerizing cycloolefin applicable to conventional ArF laser light, a crosslinkable group is not added to the positive resist.

  Specifically, the first pattern forming material according to the present invention includes a polymer obtained by polymerizing a cycloolefin having a crosslinkable group, and a thermal acid generator that generates an acid by heat. .

  According to the first pattern forming material, the etching resistance is improved by a sufficient crosslinking reaction, so that the pattern resolution in the multilayer resist process is improved. This makes it possible to extend the life of lithography using an ArF excimer laser light source, for example. In addition, the polymer formed by polymerizing the cycloolefin having a crosslinkable group is a polymer containing a hydrocarbon having a cyclic structure, and may have a constitution containing a hydrocarbon or an atom other than the hydrocarbon as a substituent.

  The second pattern forming material according to the present invention includes a polymer obtained by polymerizing a cycloolefin having a crosslinkable group and a unit of a thermal acid generator that generates an acid by heat.

  According to the second pattern-forming material, by polymerizing a cycloolefin having a crosslinkable group obtained by chemically bonding a thermal acid generator that generates an acid by heat, the probability that the distance between the crosslinkable groups approaches is increased. . For this reason, since a crosslinking reaction becomes easier, etching tolerance further improves.

  In the first or second pattern forming material, norbornene or a norbornene derivative can be used as the cycloolefin.

  In this case, the norbornene derivative is represented by the general formula [Chemical Formula 5]. However, the present invention is not limited to [Chemical Formula 5].

  Furthermore, in the first or second pattern forming material, tricyclononene or a tricyclononene derivative having a norbornene two-coordinate configuration can be used as the cycloolefin.

  In this case, the tricyclononene derivative is represented by the general formula [Chem. 6]. However, the present invention is not limited to [Chemical Formula 6].

However, n is an integer of 0 or more, R represents, -COOH, -COOR ¹ (where, ^{R 1} is an alkyl group), - OH or -OR ² (where, ^{R 2} is an alkyl group).

  In the first or second pattern forming material, an epoxy group or an oxetane group can be used as the crosslinkable group.

  Moreover, a sulfonium salt type compound, an iodonium salt type compound, or a phosphonium salt type compound is used for the unit of the thermal acid generator in the first pattern forming material or the thermal acid generator in the second pattern forming material. it can.

  In this case, triphenylsulfonium trifluoromethanesulfonic acid or triphenylsulfonium nonafluorobutanesulfonic acid can be used as the sulfonium salt type compound.

  As the iodonium salt type compound, diphenyliodonium trifluoromethanesulfonic acid or diphenyliodonium nonafluorobutanesulfonic acid can be used.

  For the phosnium salt type compound, pentaphenylphosnium trifluoromethanesulfonic acid, pentaphenylphosnium nonafluorobutanesulfonic acid, or the like can be used.

  A first pattern forming method according to the present invention comprises a pattern forming material comprising a polymer obtained by polymerizing a cycloolefin having a crosslinkable group and a thermal acid generator that generates an acid by heat on a substrate. A step of forming a lower layer film, a step of heating the lower layer film, a step of forming an intermediate layer film on the heated lower layer film, a step of forming an upper layer film made of a resist on the intermediate layer film, A step of selectively irradiating the upper layer film with exposure light to perform pattern exposure; a step of developing the upper layer film subjected to pattern exposure to form a first pattern from the upper layer film; Etching the middle layer film using the pattern as a mask to form a second pattern from the middle layer film, and etching the lower layer film using the first pattern and the second pattern as a mask, Characterized in that it comprises a step of forming a third pattern.

  According to the first pattern forming method of the present invention, since the first pattern forming material of the present invention is used, the etching resistance to the third pattern made of the lower layer film is improved. The image quality is improved.

  Further, the second pattern formation method according to the present invention is a pattern formation including a polymer obtained by polymerizing a cycloolefin having a crosslinkable group and a unit of a thermal acid generator that generates an acid by heat on a substrate. Forming a lower layer film made of a material, a step of heating the lower layer film, a step of forming an intermediate layer film on the heated lower layer film, and an upper layer film made of resist on the intermediate layer film A step of selectively irradiating the upper layer film with exposure light to perform pattern exposure, and a step of developing the upper layer film subjected to pattern exposure to form a first pattern from the resist film And etching the middle layer film using the first pattern as a mask to form a second pattern from the middle layer film, and etching the lower layer film using the first pattern and the second pattern as a mask. Accordingly, characterized in that it comprises a step of forming a third pattern from the underlying film.

  According to the second pattern forming method of the present invention, since the second pattern forming material of the present invention is used, the probability that the distance between the crosslinkable groups approaches when forming the lower layer film is increased. For this reason, since a crosslinking reaction becomes easier in the lower layer film, the etching resistance to the lower layer film is further improved. As a result, the pattern resolution in the multilayer resist process is further improved.

  In the first or second pattern forming method, the intermediate layer film preferably contains silicon.

In the first or second pattern forming method, the exposure light includes KrF excimer laser light, ArF excimer laser light, Xe ₂ laser light, F ₂ laser light, KrAr laser light, Ar ₂ laser light, extreme ultraviolet light, or electron beam Can be used. In particular, ArF excimer laser light is suitable for the present invention, and a light source having a shorter wavelength than ArF excimer laser light is preferable because it can cope with further miniaturization.

  According to the pattern forming material and the pattern forming method using the same according to the present invention, the etching resistance in the pattern forming material is improved, and the pattern resolution in the multilayer resist process is improved. Can be obtained.

(First embodiment)
FIG. 1A to FIG. 1D, FIG. 2A to FIG. 2C, and FIG. 3A regarding a pattern forming method using the pattern forming material according to the first embodiment of the present invention. This will be described with reference to FIG.

  First, an underlayer film forming material having the following composition is prepared.

Poly (5-epoxymethylnorbornene) (base polymer) …………………… 2g
Triphenylsulfonium trifluoromethanesulfonic acid (thermal acid generator) ……………………………………………………………………………………………… ……… 0.06g
Propylene glycol monomethyl ether acetate (solvent) ……………… 10g
Next, as shown in FIG. 1A, the lower film forming material is applied on the substrate 101 to form the lower film 102 having a thickness of 0.35 μm.

  Next, as shown in FIG. 1B, the lower layer film 102 is heated at a temperature of 200 ° C. for 90 seconds to crosslink the lower layer film 102.

  Next, as shown in FIG. 1C, an intermediate layer forming material (SHB-A759 manufactured by Shin-Etsu Chemical Co., Ltd.) containing silicon (Si) having a thickness of 80 nm on the cross-linked lower layer film 102 is used. An intermediate layer film 103 is formed.

  Next, as shown in FIG. 1D, the intermediate layer film 103 is heated at a temperature of 120 ° C. for 120 seconds.

  Next, as shown in FIG. 2A, an upper film 104 made of a resist material (PAR-855 manufactured by Sumitomo Chemical Co., Ltd.) having a film thickness of 100 nm is formed on the heated intermediate film 103. Thereafter, pattern exposure is performed by irradiating the upper layer film 104 with exposure light 106 made of an ArF excimer laser having an NA (numerical aperture) of 0.85 through a mask 107.

  Next, as shown in FIG. 2B, the pattern-exposed upper layer film 104 is heated at 105 ° C. for 60 seconds (post-exposure baking) and then developed with an alkali developer. Then, as shown in FIG. 2C, the first pattern 104 a is formed from the upper layer film 104.

  Next, as shown in FIG. 3A, dry etching using an etching gas containing fluorine (F) as a main component is performed on the middle layer film 103 using the first pattern 104 a as a mask, so that the middle layer film 103. A second pattern 103a is formed.

Next, as shown in FIG. 3B, dry etching using an etching gas mainly containing oxygen (O ₂ ) is performed on the lower layer film 102 using the first pattern 104a and the second pattern 103a as a mask. As a result, a third pattern 102a having a line width and a space width of 90 nm is formed from the lower layer film 102, for example. Here, the width dimension of the so-called line and space is an example, and the present invention is effective when the width dimension of the third pattern 102a is, for example, 100 nm or less.

  As described above, according to the first embodiment, the pattern forming material of the lower layer film 102 is formed, and, for example, a poly (5-epoxy) is formed on a base polymer obtained by polymerizing a cycloolefin having an epoxy group which is a crosslinkable group. Since, for example, triphenylsulfonium trifluoromethanesulfonic acid is used as the thermal acid generator that generates acid by heat using methylnorbornene), the cross-linking reaction in the lower layer film 102 proceeds sufficiently to improve etching resistance. . As a result, the resolution of the desired third pattern 102a by the multilayer resist process is improved, and the pattern shape of the third pattern 102a is improved.

(Second Embodiment)
Hereinafter, a pattern forming method using the pattern forming material according to the second embodiment of the present invention will be described with reference to FIGS. 4 (a) to 4 (d), FIG. 5 (a) to FIG. Description will be made with reference to a) and FIG.

  First, an underlayer film forming material having the following composition is prepared.

Poly (5-oxetanemethyl-6-((phenylmethyl) diphenylsulfonium trifluoromethanesulfonic acid) norbornene) (base polymer) ……………… 2g
Propylene glycol monomethyl ether acetate (solvent) ……………… 10g
Next, as shown in FIG. 4A, the lower layer film-forming material is applied onto the substrate 201 to form a lower layer film 202 having a thickness of 0.35 μm.

  Next, as shown in FIG. 4B, the lower layer film 202 is heated at a temperature of 200 ° C. for 90 seconds to crosslink the lower layer film 202.

  Next, as shown in FIG. 4C, an intermediate layer forming material (SHB-A759 manufactured by Shin-Etsu Chemical Co., Ltd.) containing silicon (Si) having a thickness of 80 nm is formed on the crosslinked lower layer film 202. An intermediate layer film 203 is formed.

  Next, as shown in FIG. 4D, the intermediate layer film 203 is heated at a temperature of 120 ° C. for 120 seconds.

  Next, as shown in FIG. 5A, an upper film 204 made of a resist material (PAR-855 manufactured by Sumitomo Chemical Co., Ltd.) having a film thickness of 100 nm is formed on the heated intermediate film 203. Thereafter, pattern exposure is performed by irradiating the upper film 204 with exposure light 206 made of an ArF excimer laser having an NA (numerical aperture) of 0.85 through a mask 207.

  Next, as shown in FIG. 5B, the upper layer film 204 that has been subjected to pattern exposure is heated for 60 seconds at a temperature of 105 ° C. (post-exposure baking), and then developed with an alkali developer. Then, as shown in FIG. 5C, a first pattern 204a is formed from the upper layer film 204.

  Next, as shown in FIG. 6A, dry etching using an etching gas containing fluorine (F) as a main component is performed on the intermediate layer film 203 using the first pattern 204a as a mask, thereby forming the intermediate layer film 203. A second pattern 203a is formed.

Next, as shown in FIG. 6B, dry etching using an etching gas mainly composed of oxygen (O ₂ ) is performed on the lower layer film 202 using the first pattern 204a and the second pattern 203a as a mask. As a result, a third pattern 202a having a line width and a space width of 90 nm is formed from the lower layer film 202, for example. Here, the width dimension of the line and space is only an example, and the present invention is effective when the width dimension of the third pattern 202a is, for example, 100 nm or less.

  As described above, according to the second embodiment, the pattern forming material of the lower layer film 202 is configured. Since poly (5-oxetanemethyl-6-((phenylmethyl) diphenylsulfonium trifluoromethanesulfonic acid) norbornene) is used as the base polymer obtained by polymerizing olefin, the crosslinking reaction in the lower layer film 202 is more improved. The etching resistance is further improved by further progress. As a result, the resolution of the desired third pattern 202a by the multilayer resist process is improved, and the pattern shape of the third pattern 202a is improved.

Incidentally, the exposure light 106 and 206, but using an ArF excimer laser beam is not limited thereto, KrF excimer laser, Xe ₂ laser, _{F 2} laser, KrAr laser, Ar ₂ laser beam, extreme ultraviolet Alternatively, an electron beam can be used. In particular, when Xe ₂ laser light, F ₂ laser light, KrAr laser light, Ar ₂ laser light, extreme ultraviolet light, or an electron beam is used, further miniaturization of the third pattern 202a can be realized.

  As the thermal acid generator, as the sulfonium salt type compound, for example, triphenylsulfonium nonafluorobutanesulfonic acid or the like can be used instead of triphenylsulfonium trifluoromethanesulfonic acid.

  Further, as the thermal acid generator, an iodonium salt type compound can be used instead of the sulfonium salt type compound. In this case, for example, diphenyliodonium trifluoromethanesulfonic acid or diphenyliodonium nonafluorobutanesulfonic acid can be used.

  Furthermore, a phosnium salt type compound can be used as the thermal acid generator. In this case, for example, pentaphenylphosnium trifluoromethanesulfonic acid or pentaphenylphosnium nonafluorobutanesulfonic acid can be used.

  The acid generator is not limited to a thermal acid generator that generates an acid by heat, and a photoacid generator that generates an acid by light can be used. In this case, for example, naphthylimide sulfonic acid trifluoromethyl ester, naphthylimide sulfonic acid nonafluorobutyl ester or naphthylimide sulfonic acid tosyl ester can be used as the photoacid generator. When a photoacid generator is used instead of the thermal acid generator, the irradiation light is applied to the lower layer films 102 and 202 in place of the heating step shown in FIGS. 1B and 4B. It is necessary to provide a light irradiation step for uniformly irradiating the light.

  The pattern forming material and the pattern forming method using the same according to the present invention improve the etching resistance of the pattern forming material and improve the pattern resolution in the multilayer resist process. It can be obtained and is useful for a pattern forming material suitable for a fine processing technique of a semiconductor device, a pattern forming method using the material, and the like.

(A)-(d) is sectional drawing which shows each process of the pattern formation method using the pattern formation material which concerns on the 1st Embodiment of this invention. (A)-(c) is sectional drawing which shows each process of the pattern formation method using the pattern formation material which concerns on the 1st Embodiment of this invention. (A) And (b) is sectional drawing which shows each process of the pattern formation method using the pattern formation material which concerns on the 1st Embodiment of this invention. (A)-(d) is sectional drawing which shows each process of the pattern formation method using the pattern formation material which concerns on the 2nd Embodiment of this invention. (A)-(c) is sectional drawing which shows each process of the pattern formation method using the pattern formation material which concerns on the 2nd Embodiment of this invention. (A) And (b) is sectional drawing which shows each process of the pattern formation method using the pattern formation material which concerns on the 2nd Embodiment of this invention. (A)-(d) is sectional drawing which shows each process of the pattern formation method by the conventional multilayer resist process. (A)-(c) is sectional drawing which shows each process of the pattern formation method by the conventional multilayer resist process. (A) And (b) is sectional drawing which shows each process of the pattern formation method by the conventional multilayer resist process.

Explanation of symbols

101 Substrate 102 Lower layer film 102a Third pattern 103 Middle layer film 103a Second pattern 104 Upper layer film 104a First pattern 106 Exposure light 107 Mask 201 Substrate 202 Lower layer film 202a Third pattern 203 Middle layer film 203a Second pattern 204 Upper layer film 204a First Pattern 206 Exposure light 207 Mask

Claims (20)

A polymer obtained by polymerizing a cycloolefin having a crosslinkable group;
A pattern forming material comprising a thermal acid generator that generates an acid by heat.   A pattern forming material comprising a polymer obtained by polymerizing a cycloolefin having a crosslinkable group and a unit of a thermal acid generator that generates an acid by heat.   The pattern forming material according to claim 1, wherein the cycloolefin is norbornene or a norbornene derivative. The pattern forming material according to claim 3, wherein the norbornene derivative is represented by a general formula [Chemical Formula 1].

However, n is an integer of 0 or more, R represents, -COOH, -COOR ¹ (where, ^{R 1} is an alkyl group), - OH or -OR ² (where, ^{R 2} is an alkyl group).   The pattern forming material according to claim 1, wherein the cycloolefin is tricyclononene or a tricyclononene derivative. The pattern forming material according to claim 5, wherein the tricyclononene derivative is represented by a general formula [Chemical Formula 2].

However, n is an integer of 0 or more, R represents, -COOH, -COOR ¹ (where, ^{R 1} is an alkyl group), - OH or -OR ² (where, ^{R 2} is an alkyl group).   The pattern forming material according to claim 1, wherein the crosslinkable group is an epoxy group or an oxetane group.   The pattern forming material according to claim 1, wherein the thermal acid generator is a sulfonium salt type compound, an iodonium salt type compound, or a phosphonium salt type compound.   The pattern forming material according to claim 2, wherein the unit of the thermal acid generator is a sulfonium salt type compound, an iodonium salt type compound, or a phosphonium salt type compound. On the substrate, forming a lower layer film made of a pattern forming material containing a polymer obtained by polymerizing a cycloolefin having a crosslinkable group and a thermal acid generator that generates an acid by heat;
Heating the lower layer film;
Forming a middle layer film on the heated lower layer film;
Forming an upper film made of a resist on the intermediate film;
A step of selectively irradiating exposure light to the upper layer film to perform pattern exposure;
Forming the first pattern from the upper film by developing the upper film subjected to pattern exposure; and
Forming the second pattern from the middle layer film by etching the middle layer film using the first pattern as a mask;
And a step of forming a third pattern from the lower layer film by etching the lower layer film using the first pattern and the second pattern as a mask. On the substrate, forming a lower layer film made of a pattern forming material including a polymer obtained by polymerizing a cycloolefin having a crosslinkable group and a thermal acid generator unit that generates an acid by heat;
Heating the lower layer film;
Forming a middle layer film on the heated lower layer film;
Forming an upper film made of a resist on the intermediate film;
A step of selectively irradiating exposure light to the upper layer film to perform pattern exposure;
Forming the first pattern from the upper film by developing the upper film subjected to pattern exposure; and
Forming the second pattern from the middle layer film by etching the middle layer film using the first pattern as a mask;
And a step of forming a third pattern from the lower layer film by etching the lower layer film using the first pattern and the second pattern as a mask.   The pattern forming method according to claim 10, wherein the cycloolefin is norbornene or a norbornene derivative. The pattern forming method according to claim 12, wherein the norbornene derivative is represented by a general formula [Chemical Formula 3].

However, n is an integer of 0 or more, R represents, -COOH, -COOR ¹ (where, ^{R 1} is an alkyl group), - OH or -OR ² (where, ^{R 2} is an alkyl group).   The pattern forming method according to claim 10, wherein the cycloolefin is tricyclononene or a tricyclononene derivative. The pattern forming method according to claim 14, wherein the tricyclononene derivative is represented by a general formula [Chemical Formula 4].

However, n is an integer of 0 or more, R represents, -COOH, -COOR ¹ (where, ^{R 1} is an alkyl group), - OH or -OR ² (where, ^{R 2} is an alkyl group).   The pattern forming method according to claim 10 or 11, wherein the crosslinkable group is an epoxy group or an oxetane group.   The pattern forming method according to claim 10, wherein the thermal acid generator is a sulfonium salt type compound, an iodonium salt type compound, or a phosphonium salt type compound.   12. The pattern forming method according to claim 11, wherein the unit of the thermal acid generator is a sulfonium salt type compound, an iodonium salt type compound, or a phosphonium salt type compound.   The pattern formation method according to claim 10, wherein the intermediate layer film includes silicon. The exposure light is KrF excimer laser light, ArF excimer laser light, Xe ₂ laser light, F ₂ laser light, KrAr laser light, Ar ₂ laser light, extreme ultraviolet light, or an electron beam. 19. The pattern forming method according to any one of items 18.

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