Resin composition for forming protective film, protective film, pattern forming method, method for manufacturing electronic device, and electronic device

Abstract

There is provided a resin composition for use in formation of a protective film to protect a substrate or a film formed on the substrate, from a developer containing an organic solvent to be used for development in pattern formation, and which contains two or more kinds of resins in which their main chain structures having a hydroxyl group are different, and contains water, a pattern forming method using the resin composition, and layered products comprising a substrate, an organic semiconductor film on the substrate, and a protective film comprising two or more kinds of resins in which their main chain structures having a hydroxyl group are different, on the organic semiconductor film.

Claims

1. A pattern forming method comprising the following steps: (1) forming an organic semiconductor film on a substrate, (2) forming a protective film using a resin composition on the organic semiconductor film, wherein the resin composition contains two or more kinds of resins in which their main chain structures having a hydroxyl group are different, and contains water, (3) forming a resist film on the protective film by an actinic ray-sensitive radiation-sensitive resin composition (I) containing a resin capable of increasing a polarity by an action of an acid to decrease the solubility in a developer containing an organic solvent, or an actinic ray-sensitive or radiation-sensitive resin composition (II) containing a conjugated diene polymer or copolymer or a cyclized product of the polymer or the copolymer, and a crosslinking agent, (4)exposing the resist film, (5) developing the resist film with a developer containing an organic solvent to form a negative type resist pattern on the resist film, (6) forming a pattern on the protective layer by using water as a developer and using the resist pattern as a mask pattern, (7) forming a pattern on the organic semiconductor film by using dry or wet etching and using the resist and protective film pattern as a mask, and (8) removing the resist pattern using a peeling solution containing an organic solvent and further removing the protective film pattern using water.

2. The pattern forming method according to claim 1, wherein the developer containing an organic solvent is a developer containing at least one organic solvent selected from the group consisting of an ester solvent, a ketone solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent.

3. The pattern forming method according claim 1, wherein the peeling solution containing an organic solvent is a peeling solution containing at least one organic solvent selected from the group consisting of an alcohol solvent, an ether solvents and a hydrocarbon solvent.

4. A method for manufacturing an electric device, comprising the pattern forming method according to claim 1.

5. A layered product comprising: a substrate, an organic semiconductor film on the substrate, and a protective film comprising two or more kinds of resins in which their main chain structures having a hydroxyl group are different, on the organic semiconductor film.

6. A layered product comprising: a substrate, an organic semiconductor film on the substrate, a protective film comprising two or more kinds of resins in which their main chain structures having a hydroxyl group are different, on the organic semiconductor film, and a resist film comprising an actinic ray-sensitive or radiation-sensitive resin composition (I) containing a resin capable of increasing a polarity by an action of an acid to decrease the solubility in a developer containing an organic solvent, on the protective film.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not intended to be limited to the Examples below. Unless specified otherwise, parts and % are per mass.

Examples 1-5 and Comparative Examples 1 to 3

(2) [Preparation of the Resin Composition for Forming a Protective Film]

(3) The components shown in Table 1 were dissolved in water (and a mixed solvent) to prepare an aqueous solution for each component, and a resin composition for forming a protective film was prepared. The solid content concentration of each resin composition was adjusted appropriately in a range of 2 to 14% by mass.

(4) [Table 1]

(5) TABLE-US-00001 TABLE 1 Resin Additive Water Solvent Content Content Content Content Content Kind (g) Kind (g) Kind (g) (g) Kind (g) Composition 1 A1 14.1075 A3 0.7425 C1 0.15 85 Composition 2 A1 10.395 A3 4.455 C1 0.15 85 Composition 3 A1 14.1075 A3 0.7425 C2 0.15 84.5 G4 0.5 Composition 4 A1 14.1075 A3 0.7425 C2 0.15 82 G4 3 Composition 5 A2 1.881 A3 0.099 C1 0.02 98 Composition 6 A1 14.85 C1 0.15 85 Composition 7 A2 1.98 C1 0.02 85 Composition 8 A3 14.85 C1 0.15 85

(6) Components and abbreviations in Table 1 above are as follows.

(7) [Two Kinds of Resins in which Main Chain Structures Having Hydroxyl Group are Different]

(8) From the following A1 to A3, two kinds of resins are appropriately selected and used. A1: Pullulan (weight average molecular weight: 200,000; Hayashibara Co., Ltd.) A2: Water-soluble cellulose (weight average molecular weight: 200,000; Daicel FineChem Co., Ltd.; HEC Daicel) A3: Polyvinyl alcohol (saponification degree: 99 mol % or more, polymerization degree: 500; Kuraray Co., Ltd.)
[Additives (Surfactant)] C1: Emma Rex 710 (Nihon Emulsion Co., Ltd.) C2: Emma Rex 310 (Nihon Emulsion Co., Ltd.)
[Solvent] G4: Dipropylene glycol monomethyl ether
[Formation of a Protective Film Using the Above-described Resin Composition on Bare Silicon]

(9) The resin compositions described in Table 1 above were coated on 4-inch bare silicon substrate with a spin coater (1,200 rpm, 30 seconds) and then baked at 100 C./60 seconds on a hot plate to obtain a protective film with an average film thickness of 1000 nm. Thereafter, the thickness of the protective film was measured at 15 points using Lambda Ace (manufactured by Dainippon Screen Co. Ltd.) as the substrate. The difference between the maximum and minimum values of the measured film thickness (film thickness range) is shown in Table 2. That is, a case where the difference is 100 nm or less is regarded as A, and a case where the difference exceeds 100 nm is regarded as B. A case where there is a release after visual confirmation is regarded as B, and a case regarded there is no release is regarded as A in Table 2.

(10) [Formation of a Protective Film Using the Above-described Resin Composition on the Organic Semiconductor Film]

(11) As an organic semiconductor, concentration 10 mL of P3HT (manufactured by Merck Co., Ltd.) chlorobenzene solution 10 mL having a concentration of 20 g/L and 10 mL of [60] PCBM (manufactured by Solenne Co.) chlorobenzene solution having a concentration of 14 g/L were mixed, applied on 4-inch bare silicon substrate using a spin coater (1,200 rpm, 30 seconds) and then dried at 140 C./15 minutes on a hot plate to form an organic semiconductor film having a thickness of 100 nm. The wafer formed with the organic semiconductor film on a substrate was regarded as a wafer 1. The resin compositions described in Table 1 was coated on the wafer 1 by a spin coater (1,200 rpm, 30 seconds) and then baked at 100 C. for 60 seconds to form a wafer 2 in which the protective film having a thickness of 1,000 nm are formed on the organic semiconductor film. Further, the case in which there is a coating unevenness, such as release or striation (phenomenon in which concavity and convexity of the film thickness is radically produced) by visual observation is regarded as Bin Table 2, and the case in which there are no releasing and coating unevenness is regarded as A in Table 2.

(12) Based on the result of the comprehensive determination, a case where both results on the bare silicon and on the organic semiconductor are determined as A is regarded as pass, and a case where any one is determined as B is regarded as fail in Table 2.

(13) [Table 2]

(14) TABLE-US-00002 TABLE 2 On organic On bare semiconductor silicon substrate substrate Film thickness Peeling/uneven Result of Kind rage peeling coating Determination Example 1 Composition 1 A A A Pass Example 2 Composition 2 A A A Pass Example 3 Composition 3 A A A Pass Example 4 Composition 4 A A A Pass Example 5 Composition 5 A A A Pass Comparative Composition 6 A B B Fail Example 1 Comparative Composition 7 B A B Fail Example 2 Comparative Composition 8 B A B Fail Example 3

(15) As is apparent from the results shown in Table 2, Comparative Examples 1 to 3 in which a protective film was obtained using a resin composition containing one resin having a hydroxyl group showed that the thickness range is large on a bare silicon, but a release occurs and a releasing or coating unevenness is generated on the organic semiconductor film.

(16) On the other hand, Examples 1 to 5 in which a protective film was obtained by mixing two kinds of resins in which the chain structures having hydroxyl group are different showed that the film thickness range is small on a bare silicon, no a release is presented, and a releasing or uneven coating unevenness is not generated on the organic semiconductor film.

Examples 6-9, Comparative Examples 4 and 5

(17) [Pattern Formation Using the Actinic Ray-sensitive or Radiation-sensitive Resin Composition (I) Containing a Resin Capable of Increasing a Polarity by an Action of an Acid to Decrease the Solubility in a Developer Containing an Organic Solvent]

(18) The actinic ray-sensitive or radiation-sensitive resin composition shown in Tables 3 and 4 below was coated on the 4-inch (8-inch in a case of KrF exposure) wafer 2 and then baked 100 C. for 60 seconds to form a wafer 3 in which the resist film having a thickness of 500 nm are formed on the wafer 2.

(19) Next, the wafer 3 was subjected to exposure (exposure amount: 120 mJ/cm.sup.2) under optical conditions of NA: 0.57, : 0.60 using an i-ray projection exposure apparatus NSR2005i9C (manufactured by Nikon), or subjected to exposure (exposure amount: 25 mJ/cm.sup.2) under optical conditions of NA: 0.60, : 0.70 using KrF projection exposure apparatus PAS5500/850 (manufactured by ASML, Inc.), and exposed through a binary mask of 1:1 line-and-space pattern with a line width of 25 m. Thereafter, it was baked at 110 C. for 60 seconds, developed with a developer described in Table 5 below for 15 seconds and spin-dried to obtain a resist pattern of 1:1 line-and-space pattern with a line width of 25 m. Further, it was then developed with water (a developer solution 2 described in Table 5 below) for 30 seconds and spin-dried to obtain a pattern of 1:1 line-and-space a line width of 25 m in the same manner as the resist pattern on the protective film.

(20) TABLE-US-00003 TABLE 3 Acid- decomposable Acid resin generator Additives Solvent Content Content Content Content Content Content Kind (g) Kind (g) Kind (g) Kind (g) Kind (g) Kind (g) Composition 9 D1 9.698 E1 0.25 F3 0.05 F1 0.002 G1 90 Composition 10 D2 5.566 E2 0.404 F2 0.018 F1 0.012 G1 47 G3 47

(21) Components and abbreviations in Table 3 are as follows.

(22) [Resin Capable of Increasing a Polarity by an Action of an Acid to Decrease the Solubility in the Developer Solution Containing the Organic Solvent]

(23) For resins D1 and D2, the repeating unit (unit), composition ratio (molar ratio), weight average molecular weight (Mw), and polydispersity are shown.

(24) ##STR00060##
[Acid Generator (PAG)]

(25) ##STR00061##
[Additives]

(26) ##STR00062##
[Solvent] G1: propylene glycol monomethyl ether acetate (PGMEA) G3: cyclohexanone

(27) TABLE-US-00004 TABLE 4 Crosslinking Reaction Resin compound initiator Additive Solvent Content Content Content Content Content Kind (g) Kind (g) Kind (g) Kind (g) Kind (g) Composition 11 III 9.44 H2 9.44 J1 1 F2 0.12 G1 80

(28) Components and abbreviations in Table 4 above are as follows.

(29) [Crosslinking Compound, and Resin]

(30) ##STR00063##
[Photoinitiator]

(31) ##STR00064##
[Confirmation of Pattern Formation]

(32) The combination of each resin composition for forming a protective film and the actinic ray-sensitive or radiation-sensitive resin composition, the exposure light source and type of the developer solution are described in Table 5 below. A case where the resist pattern could be formed is regarded as A, and a case where the pattern was not formed is regarded as B.

(33) Further, after the pattern formation, the removal of the resist pattern in PGME or 4-methyl-2-pentanol (MIBC) was evaluated at room temperature for 60 seconds. The results are also listed in Table 5. A case where the releasing was possible is regarded as A, and a case where the releasing was not possible or the case where releasable pattern could not be formed is regarded as B.

(34) TABLE-US-00005 TABLE 5 Radiation- sensitive Exposure Resist Releasing Releasing Resin resin light Developer Developer pattern property property composition composition source 1 2 formation PGME MIBC Example 6 Composition 1 Composition 9 i-ray K2 K3 A A B Example 7 Composition 1 Composition 10 KrF K1 K3 A A A Comparative Composition 1 Composition 11 i-ray K2 K3 A B B Example 4 Example 8 Composition 3 Composition 9 i-ray K2 K3 A A B Example 9 Composition 3 Composition 10 KrF K1 K3 A A A Comparative Composition 3 Composition 11 i-ray K2 K3 A B B Example 5

(35) Among the Table 5 above, Comparative Examples 4 and 5 are comparative examples of Claim 8.

(36) Abbreviations in the Table 5 above are as follows.

(37) [Developer]

(38) K1: butyl acetate K2: 2-heptanone K3: water

(39) As is apparent from the results shown in Table 5, Comparative Examples 4 and 5 using a crosslinkable actinic ray-sensitive or radiation-sensitive resin composition containing the resin and the crosslinkable compound showed that the pattern, formability was excellent and the releasing property is inferior.

(40) On the other hand, Examples 6-9 using a protective film of the present invention and also using the actinic ray-sensitive or radiation-sensitive resin composition containing an acid-decomposable resin showed that both pattern formability and releasing property are excellent.

Examples 10-15

(41) [Pattern Formation Using the Actinic Ray-sensitive or Radiation-sensitive Resin Composition (II) Containing a Conjugated Diene Polymer or a Cyclized Product Thereof, and a Crosslinking Agent]

(42) The compositions described in Table 6 below was spin-coated on the wafer 2 which is a laminate to form a protective film on the organic semiconductor film, from Examples 1 to 5 and baked at 110 C. for 60 seconds to form a wafer 3 in which a resist film with a film thickness of 1.5 m was formed on the wafer 2.

(43) Next, the wafer 3 was subjected to contact exposure (exposure amount: 120 mJ/cm.sup.2) under optical conditions of NA: 0.57, : 0.60 using an i-ray projection exposure apparatus NSR 2005i9C (manufactured by Nikon), and exposed through a binary mask of 1:1 line-and-space pattern with a line width of 2 m. Thereafter, it was baked at 110 C. for 60 seconds and then developed with a developer 1 described in Table 7 below at room temperature for 15 seconds and spin-dried to obtain a resist pattern of a line-and-space. Thereafter, it was developed with water (developer 2 shown in Table 7 below) for 30 seconds and spin-dried to obtain a pattern of a line-and-space having a line width 25 m in the same manner as the resist patter on the protective film.

(44) TABLE-US-00006 TABLE 6 Composition 12 Cyclized isoprene 2,6-di(para-azidobenxal)-4- 4,4-butadiene-bis(6-tert- Xylene rubber methyl cyclohexanone butyl-m-cresol) 26 parts by mass 0.5 parts by mass 0.1 parts by mass 74 parts by mass Composition 13 Cyclized isoprene 2,6-di(para-azidobenzal)-4- 4,4-butadiene-bis(6-tert- Naththalazine Xylene rubber methyl cyclohexanone butyl-m-cresol) 12 parts by mass 0.5 parts by mass 0.1 parts by mass 0.5 parts by mass 87 parts by mass Composition 14 Cyclized isoprene 2,6-di(para-azidobenzal)-4- 4,4-butadiene-bis(6-tert- Xylene rubber methyl cyclohexanone butyl-m-cresol) 12 parts by mass 0.5 parts by mass 0.06 parts by mass 87 parts by mass Composition 15 Cyclized isoprene 2,6-di(para-azidobenzal)-4- Diazoaminobenzene Oil Yellow Xylene rubber methyl cyclolhexanone SS special 10 parts by mass 0.3 parts by mass 0.15 parts by mass 0.1 parts by mass 89 parts by mass Composition 16 Cyclized isoprene 2,6-di(para-azidobenzal)-4- Xylene rubber methyl cyclohexanone 11 parts by mass 0.4 parts by mass 88 parts by mass Composition 17 Cyclized isoprene 2,6-di(para-azidobenzal)-4- Diazoaminobenzene Kaycoll C Oil Yellow SS Xylene rubber methyl cyclohexanone special 7 parts by mass 0.2 parts by mass 0.1 parts by mass 0.2 parts by mass 0.1 parts by mass 92 parts by mass

(45) Components and abbreviations in Table above are as follows.

(46) [Cyclized Product of the Conjugated Diene-based Polymer]

(47) Cyclized isoprene rubber: weight average molecular weight: 4,9000, polydispersity (weight average molecular weight/number average molecular weight: 1.7, and cyclization: 65%.

(48) [Crosslinking Agent]

(49) 2,6-di(para-azidobenzal)-4-methyl cyclohexanone

(50) [Polymerization Initiator]

(51) Diazoaminobenzene

(52) [Antioxidant]

(53) 4,4-butadiene-bis(6-tert-butyl-m-cresol)

(54) [Colorant]

(55) Naphthalazine

(56) Oil Yellow SS special (manufactured by Shirado Chemistry)

(57) Keycall C (manufactured by Nippon Soda)

(58) [Solvent]

(59) Xylene

(60) [Confirmation of Pattern Formation]

(61) The combination of each resin composition for forming a protective film and the actinic ray-sensitive or radiation-sensitive resin composition, and type of the developer are described in Table 7 below. A case where the resist pattern could be formed is regarded as A, and a case where the pattern was not formed is regarded as B.

(62) Further, after a pattern formation, the releasing property of the resist pattern in PGME or 4-methyl-2-pentanol (MIBC) was evaluated at room temperature for 60 seconds. The results are also listed in Table 7. A case where the releasing was made is regarded as A, and a case where the releasing was not possible or a case where releasable pattern could not be formed is regarded as B.

(63) TABLE-US-00007 TABLE 7 Resin Resin composition composition for containing a Resist Releasing Releasing forming a cyclized Developer Developer pattern property property protective film isoprene rubber 1 2 formation PGME MIBC Example 10 Composition 1 Composition 12 K1 K3 A A A Example 11 Composition 2 Composition 13 K2 K3 A A A Example 12 Composition 3 Composition 14 K1 K3 A A A Example 13 Composition 4 Composition 15 K2 K3 A A A Example 14 Composition 5 Composition 16 K1 K3 A A A Example 15 Composition 5 Composition 17 K2 K3 A A A

(64) In abbreviations in Table 7, the developers K1 to K3 are as described above.

(65) As apparent from the results shown in Table 7, Examples 10 to 15 which use the protective film of the present invention, and also use the actinic ray-sensitive or radiation-sensitive resin composition comprising a cyclized isoprene rubber and a crosslinking agent showed that both pattern formability and releasing property are excellent.

INDUSTRIAL APPLICABILITY

(66) According to the present invention, there is provided a resin composition for forming protective film, a protective film, and a pattern forming method, which can form the protective film, having uniform film thickness without occurrence of a release or coating irregularity, on a substrate or on a film formed on the substrate, thereby forming fine and uniform pattern by a developer containing an organic solvent.

(67) Also, according to the pattern-forming method of the present invention, the formed resist and protective film pattern may be used a mask to form a desired pattern on the organic semiconductor film, and subsequently, the resist and protective film used as a mask may be removed without damaging on the organic semiconductor film of the underlying layer.

(68) In addition, there is provided the electronic device manufactured by the method for manufacturing the electronic device comprising the pattern forming method.

(69) While the invention has been described with reference to details or specific embodiments, it will be apparent to those skilled in the art that various changes and modifications may be made thereto without departing from the spirit and scope of the invention.

(70) This application is based on Japanese Patent Application filed on Oct. 19, 2012 (Japanese Patent Laid-Open Publication No. 2012-232416) and Japanese Patent Application filed on Aug. 26, 2013 (Japanese Patent Laid-Open Publication No. 2013-174743), the contents of which are incorporated herein by reference.