WO2010041795A1 - Positive photosensitive resin composition - Google Patents

Positive photosensitive resin composition Download PDF

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Publication number
WO2010041795A1
WO2010041795A1 PCT/KR2008/007907 KR2008007907W WO2010041795A1 WO 2010041795 A1 WO2010041795 A1 WO 2010041795A1 KR 2008007907 W KR2008007907 W KR 2008007907W WO 2010041795 A1 WO2010041795 A1 WO 2010041795A1
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WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
same
chemical formula
positive photosensitive
Prior art date
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PCT/KR2008/007907
Other languages
French (fr)
Inventor
Yong-Sik Yoo
Hyun-Yong Cho
Doo-Young Jung
Jong-Hwa Lee
Ji-Young Jeong
Min-Kook Chung
Kil-Sung Lee
Original Assignee
Cheil Industries Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from KR1020080108990A external-priority patent/KR101015857B1/en
Application filed by Cheil Industries Inc. filed Critical Cheil Industries Inc.
Priority to CN2008801314494A priority Critical patent/CN102177469A/en
Publication of WO2010041795A1 publication Critical patent/WO2010041795A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides

Definitions

  • the present invention relates to a positive photosensitive resin composition. More particularly, the present invention relates to a positive photosensitive resin composition having excellent heat resistance and being capable of providing high sensitivity and high-resolution fine patterns.
  • a positive photosensitive resin composition having excellent heat resistance and being capable of providing high sensitivity and high-resolution fine patterns.
  • semiconductor and liquid crystal display devices have tended to require higher integration, higher confidence, and higher density, researchers have actively undertaken studies on using organic materials having high purity and workability. Therefore, a surface protective layer and an interlayer insulating layer of a semiconductor device require a resin composition having excellent heat resistance and excellent electrical and mechanical characteristics.
  • a resin composition that is capable of forming high resolution fine patterns has drawn attention.
  • Forming patterns with a resin composition for a surface protective layer and an interlayer insulating layer having excellent heat resistance and excellent electrical and mechanical characteristics as well as being capable of forming fine high resolution patterns is a core technique, and it allows creation of an ultra-highly integrated semiconductor.
  • the conventional positive photosensitive resin composition is prepared by adding esterified quinonediazide having photosensitivity to a polyamide polymer, or by covalent-bonding a polyamide polymer with quinonediazide.
  • the general pattern forming process using the composition includes exposing the photosensitive resin composition to light having a certain wavelength with a patterning mask.
  • the quinonediazide compound is chemically changed to convert it to carboxylic acid.
  • the exposed layer is contacted with a certain material (traditionally, an aqueous alkali developing solution).
  • a certain material traditionally, an aqueous alkali developing solution.
  • the part of the composition including the converted carboxylic acid increases solubility to the alkali developing solution, so as to be selectively developed thereby.
  • the patterned layer is then heated to provide a cured pattern.
  • the protective layer it should be designed to provide a higher amount of aromatic compound, a higher polymer molecular weight, a higher degree of cross-linking, and lower fluidity, but in order to improve the photo-characteristics, it should be designed to provide a lower amount of aromatic compound, a lower polymer molecular weight, a lower degree of cross-linking, and higher fluidity, so it is not easy to develop a material satisfying the conflicting characteristics.
  • the soluble polyimide can improve the mechanical layer characteristics, it deteriorates the transmittance of the wavelength of exposure light due to the closed ring structure, so it finally decreases the resolution and sensitivity, and the characteristics for forming fine patterns are deteriorated.
  • the conventional photosensitive resin composition still has problems of not satisfying the requirements of a finer pattern and improved mechanical characteristics needed for the improvement of the highly integrated semiconductor device. Accordingly, there is a need to develop a new form of photosensitive resin material that is required to overcome the limits of the conventional material.
  • DISCLOSURE [Technical Problem]
  • An exemplary embodiment of the present invention provides a positive photosensitive resin composition.
  • Another embodiment of the present invention provides a positive photosensitive resin having excellent heat resistance and being capable of forming a fine pattern having high sensitivity and high resolution.
  • a further embodiment of the present invention provides a method of making a photosensitive pattern using the photosensitive resin composition.
  • a positive photosensitive resin composition includes (A) a polyamide polymer having the following Formula 1 , (B) an esterified quinone diazide compound, (C) a phenol group-included compound, and (D) a solvent. [Chemical Formula 1]
  • Xi and X 2 are the same or different and are independently a divalent to quadrivalent organic group
  • Yi and Y 2 are the same or different and are independently a divalent to hexavalent organic group
  • Ri and R 2 are the same or different and are independently hydrogen or a C1 to C5 organic group
  • Ei and E 2 are the same or different and are independently hydrogen, or a moiety derived from one selected from the group consisting of monocarboxylic acid, and an active derivative thereof, provided that both Ei and E 2 are not hydrogen, mi and m 2 are the same or different and are independently 0 to 100, and mi+m 2 ranges from 5 to 100.
  • a method of making a photosensitive pattern includes coating the above positive photosensitive resin composition on a supporting substrate and drying it to a resin composition layer, subjecting the resin composition layer to exposure, subjecting the exposed resin composition layer to development with an alkali development solution, and subjecting the developed resin composition layer to heating.
  • a semiconductor electronic component for a semiconductor including a photosensitive resin layer made using the positive photosensitive resin composition is provided.
  • the positive photosensitive resin composition includes one end or both ends of polyamide encapsulated by an alkyl group, an aryl group, an alicyclic group, or a heterocyclic group derived from a compound selected from the group consisting of monocarboxylic acid and activated derivatives, so as to maximize a dissolubility rate difference between the non-exposed part and the exposed part. Accordingly, when the pattern is formed with the photosensitive resin composition, the developing rate is increased at the exposed part, so that it is possible to form a high resolution pattern. After the curing process, the degree of close-ring and the degree of cross-linking are improved to provide a photosensitive resin layer having excellent film characteristics.
  • FIG. 1 is a view showing a process of making a pattern using a positive photosensitive resin composition.
  • semiconductor device 2 photosensitive resin composition layer
  • the photosensitive resin composition according to one embodiment of the present invention includes (A) a polyamide polymer represented by the following Formula 1, (B) an esterified quinone diazide compound, (C) a phenol group-included compound, and (D) a solvent.
  • substituted refers to one substituted with at least a substituent including a halogen, an alkyl, an aryl, an alkoxy, an amino, or an alkenyl.
  • an alkyl refers to a C1 to C30 alkyl, and preferably a C1 to C15 alkyl
  • the term “an aryl” refers to a C6 to C30 aryl, and preferably a C6 to C18 aryl
  • the term “an alkenyl” refers to a C2 to C30 alkenyl, and preferably a C2 to C15 alkenyl
  • the term “alkoxy” refers to a C1 to C30 alkoxy, and preferably a C1 to C15 alkoxy
  • the term "alicyclic group” refers to a C3 to C40 cycloalkyl or a C3 to C40 cycloalkenyl, and preferably a C3 to C24 cycloalkyl or a C3 to C24 cycloalkenyl.
  • the terms “alicyclic group” refers to a C3 to C40 cycloalkyl or a C3 to C40 cycl
  • divalent to quadrivalent organic group and “divalent to hexavalent organic group” respectively refer to an organic group including 2 to 4 functional groups and an organic group including 2 to 6 functional groups.
  • the functional groups are substituents excluding hydrogen.
  • heterocycle refers to one selected from the group consisting of “heteroaryl”, “heterocycloalkyl”, “heterocycloalkenyl”, and “heterocycloalkynyl”.
  • hetero-compound refers to a compound including at least one atom selected from the group consisting of N, O, P, and Si instead of carbon.
  • the polyamide polymer is represented by the following Formula 1. [Chemical Formula 1]
  • Xi and X 2 are the same or different and are independently a divalent to quadrivalent organic group
  • Yi and Y 2 are the same or different and are independently a divalent to hexavalent organic group
  • Ri and R 2 are the same or different and are independently hydrogen or a C1 to C5 organic group
  • Ei and E 2 are the same or different and are independently hydrogen, or a moiety derived from one selected from the group consisting of monocarboxylic acid and an active derivative thereof, provided that both Ei and E 2 are not hydrogen, and preferably Ei and E 2 are an alkyl, an aryl, an alicyclic group, or a heterocyclic group
  • mi and m 2 are the same or different and are independently 0 to 100, and mi+m 2 ranges from 5 to 100.
  • the polyamide polymer represented by the above Formula 1 is prepared as follows: a diamine monomer is reacted with an acid monomer selected from the group consisting of tetracarboxylic acid dianhydride, dicarboxylic acid anhydride, dicarboxylic acid, and active derivatives thereof to obtain a reaction product, and the reaction product is reacted with an end-capping monomer to convert an amine group of the reaction product to an amide group.
  • an acid monomer selected from the group consisting of tetracarboxylic acid dianhydride, dicarboxylic acid anhydride, dicarboxylic acid, and active derivatives thereof to obtain a reaction product
  • the reaction product is reacted with an end-capping monomer to convert an amine group of the reaction product to an amide group.
  • the method of preparing the polyamide polymer is described in more detail.
  • the diamine monomer may be represented by X(NH2)2, wherein X is the same as Xi or X 2 in Chemical Formula 1.
  • Xi and X 2 of Chemical Formula 1 are derived from the diamine monomer.
  • X may be represented by the following Formulae 2 to 7, but is not limited thereto.
  • Zi to Zi 5 are the same or different, and are independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl, a hydroxy, a carboxylic acid group, and a thiol, and
  • Ai to A 6 are the same or different, and are independently selected from the group consisting of CR 3 R 4 , S, O, SO2, CO, CONH, and a single bond, where
  • R 3 and R 4 are the same or different and are independently selected from the group consisting of hydrogen, or a substituted or unsubstituted alkyl, and preferably a fluoroalkyl.
  • the diamine monomer may include an aromatic diamine, an alicyclic diamine, and an aliphatic diamine.
  • diamine monomer examples include benzidine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether,
  • the diamine monomer may preferably be selected from the group consisting of 4,4'-diaminodiphenylether, 4,4'-diaminodiphenyl methane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-diamino-4,4'-dihydroxysulfone, and mixtures thereof.
  • a silicon-included diamine monomer may be used along with the diamine monomer.
  • the silicon-included diamine monomer increases adherence relative to a substrate.
  • Examples of the silicon-included diamine monomer include bis(4-aminophenyl)dimethylsilane, bis(4-aminophenyl)tetramethylsiloxane, bis(p-aminophenyl)tetramethyldisiloxane, bis(gamma-aminopropyl)tetramethyldisiloxane, 1 ,4-bis-(gamma-aminopropyldimethylsilyl)benzene,
  • a preferable silicon-included diamine monomer includes bis(4-aminophenyl)tetramethylsiloxane, bis(p-aminophenyl)tetramethyldisiloxane, or a mixture thereof.
  • a copolymer of which a ratio of a silicon-containing diamine monomer to a diamine monomer not containing silicon is between 0.1 and 10 wt%.
  • the acid monomer that reacts with the diamine monomer may be selected from the group consisting of tetracarboxylic acid dianhydride, dicarboxylic acid anhydride, dicarboxylic acid, and an active derivative thereof. Yi and Y 2 of Chemical Formula 1 are derived from the acid monomer.
  • the tetracarboxylic acid dianhydride may be represented by the following Formula 8, but is not limited thereto. [Chemical Formula 8]
  • Y is the same as Y 1 or Y 2 in Chemical Formula 1.
  • the dicarboxylic acid monomer may be represented by Y(COOH) 2 , wherein Y is the same as Yi or Y 2 in Chemical Formula 1.
  • the active derivative of the dicarboxylic acid monomer may be represented by Y(COFC) 2 , where Y is the same as Y 1 or Y 2 in Chemical Formula 1 , and K' is a moiety obtained by reacting Y(COOH) 2 and a halide, or Y(COOH) 2 and 1-hydroxy-1 ,2,3-benzotriazole.
  • the following Formulae 9 to 16 may be derived from the acid monomer.
  • Ki to K 21 are the same or different, and are independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl, a hydroxy, a carboxylic acid group, a thiol, and COOR 5 , where R 5 is hydrogen or a C1 to C5 alkyl, and
  • Bi to B 6 are the same or different, and are independently selected from the group consisting of -CR 6 Rr-, -S-, -O-, -SO 2 -, -CO-, -CONH-, and a single bond, where R 6 and R 7 are the same or different and are independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl.
  • the substituted alkyl preferably is a fluoroalkyl, and the unsubstituted alkyl is preferably a methyl.
  • the acid monomer may be tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, S.S'A ⁇ -biphenyltetracarboxylic acid dianhydride, 2,3,3',4-biphenyltetracarboxylic acid dianhydride,
  • the acid monomer may be a dicarboxylic acid active derivative such as a carbonyl halide derivative and an active ester derivative obtained by reacting an acid monomer and 1-hydroxy-1 ,2,3-benzotriazole.
  • the active derivative examples include 4,4-oxydibenzonylchloride, phthalic dichloride, diphenyloxydicarboxylic acid chloride, bis(phenylcarboxylic acid chloride)sulfone, bis(phenylcarboxylic acid chloride)ether, bis(phenylcarboxylic acid chloride)phenone, phthalic carboxylic acid dichloride, diphenyloxydicarboxylate benzotriazole, and the like.
  • Preferable acid monomers include 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, bis(3,4-dicarboxylphenyl)ether dianhydride, diphenyloxydicarboxylic acid chloride, phthalic carboxylic acid dichloride, and the like, but are not limited thereto.
  • the polyamide polymer represented by Chemical Formula 1 can be a copolymer in which two or more monomers are copolymerized within a range to not damage the photo-characteristics, the layer characteristic, and water-solubility of a homopolymer or polymer consisting of amide bond units.
  • the copolymer may include various patterns, for example a random copolymer, a block copolymer, or a graft copolymer, but in one embodiment, it includes a random copolymer.
  • the end-capping monomer reacting with the reaction product obtained by reacting an acid monomer with a diamine monomer may include a compound selected from the group consisting of monocarboxylic acid and active derivatives thereof.
  • the monocarboxylic acid may be any carboxylic acid, and particularly an alicyclic monocarboxylic acid such as cyclohexyl carboxylic acid, norbornane carboxylic acid, adamantyl carboxylic acid, isobornyl carboxylic acid, and norbornene carboxylic acid, or active derivatives thereof.
  • the monocarboxylic acid can be used singularly or in combination.
  • the active derivative of the carboxylic acid includes cyclohexyl carboxyl chloride, norbornane carboxyl chloride, norbornene carboxyl chloride, adamantyl carboxylic acid chloride, isobornyl carboxylic acid chloride, 4-nadimido benzoyl chloride, cyclohexyl carboxylate benzotriazole, norbornene carboxylate benzotriazole, and the like.
  • the molecular weight of the polyamide polymer may be selected within a range so as to not damage the advantage of the present invention, but in one embodiment, the weight average molecular weight (Mw) ranges from 500 to 500,000, and in another embodiment, it ranges from 1000 to 50,000 in order to secure the effective dissolubility and coating property and to maximize the pattern-forming effect after patterning. When the weight average molecular weight is within the range, it is possible to provide sufficient physical properties and excellent solubility to the organic solvent, so as to make it convenient to handle.
  • Mw weight average molecular weight
  • esterified quinone diazide compound functions as a photo-active compound (PAC), and preferably includes a 1 ,2-benzoquinone diazide or 1 ,2-naphtoquinone diazide structure. These compounds are described in U.S. Patent Nos. 2,772,975, 2,797,213, and 3,669,658.
  • the esterified quinonediazide compound may include the compound represented by the following Formulae 17 to 19, but is not limited thereto. [Chemical Formula 17]
  • Gi to G 4 are the same or different, and are independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl, and the alkyl is preferably a methyl, ni to n 9 are the same or different, and are independently an integer ranging from 1 to 3, m 3 is an integer of 0 to 3,
  • Di to D 9 are the same or different, and are independently OQ, and
  • Q is hydrogen, or is represented by the above Formula 18-1 or 18-2.
  • the ratio that Q is hydrogen that is to say, the substitution ratio of OH in an aromatic ring, ranges from 0 to 90mol%, and is preferably 30 to 80mol%.
  • the esterified quinonediazide compound may be included at 1 to 50 parts by weight based on 100 parts by weight of the polyamide polymer, and in another embodiment, it ranges from 5 to 30 parts by weight.
  • the amount of the esterified quinonediazide compound is within the range, the pattern is well-formed without a residue from exposure, and it is possible to prevent a film thickness loss during development and to provide a good pattern.
  • the phenol group-included compound functions as a dissolution inhibitor to control a dissolution rate difference of an exposed part and a non-exposed part.
  • the phenol group-included compound includes 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, or 2,6-diacetoxymethyl-p-cresol, but is not limited thereto.
  • the phenol group-included compound may be represented by the following Formulae 20 to 25, but is not limited thereto. [Chemical Formula 20]
  • R 8 to Rio are the same or different, and are independently hydrogen, or a substituted or unsubstituted alkyl
  • Rn to Ri 5 are the same or different, and are independently selected from the group consisting of H, OH, and a substituted or unsubstituted alkyl, and the alkyl is preferably CH 3 , and nio is an integer of 1 to 5.
  • Ri 6 to R 21 are the same or different, and are independently selected from the group consisting of H, OH, and a substituted or unsubstituted alkyl,
  • a 4 is CR 1 R" or a single bond, where R' and R" are the same or different, and is independently hydrogen, or a substituted or unsubstituted alkyl, and the alkyl is preferably CH 3 , and nii+ni2+ni 3 and n-u+n-is+ni ⁇ are the same or different, and are independently integers of 5 or less.
  • R 22 to R 24 are the same or different, and are independently hydrogen, or a substituted or unsubstituted alkyl, ni 7 , n-i 8 , and n 2 i are the same or different, and are independently integers of 1 to 5, and mg and n 2 o are the same or different, and are independently integers of 0 to 4.
  • R 2 ⁇ to R 27 are the same or different, and are independently selected from the group consisting of hydrogen, OH, and a substituted or unsubstituted alkyl, and rt ⁇ to ri2 6 are the same or different, and are independently integers of 1 to 4, provided that n22 + n24 and n23+n2 ⁇ are independently integers of 5 or less.
  • R 28 is a substituted or unsubstituted alkyl, and is preferably CH 3 ,
  • R 29 to R 31 are the same or different, and are independently hydrogen, or a substituted or unsubstituted alkyl
  • n 27 , n 29 , and n 3 i are the same or different, and are independently integers of 1 to 5
  • n2 8 , n 3 o, and n 3 2 are the same or different, and are independently integers of 0 to 4, provided that n27+n28, n29+n3o, and n3i+n 3 2 are independently integers of 5 or less.
  • R 3 2, R 33 , and R 3 4 are the same or different, and are independently a substituted or unsubstituted alkyl, and preferably CH 3 ,
  • R 35 to R 38 are the same or different, and are independently hydrogen, or a substituted or unsubstituted alkyl
  • ri 33 , n 35 , and n 39 are the same or different, and are independently integers of 1 to 5
  • ri 34 , ri 36 , and n 38 are the same or different, and are independently integers of 0 to 4
  • n 37 is an integer of 1 to 4, provided that n 33 +n 34 , n 35 +n 36 , and n 38 +n 39 are independently integers of 5 or less.
  • the phenol group-included compound is included at 0.1 to 30 parts by weight based on 100 parts by weight of a polyamide polymer.
  • the amount of the phenol group-included compound is within the range, it does not cause deterioration of sensitivity during the development, and it suitably increases the dissoluble rate of the non-exposed part to provide a good pattern. In addition, it is not precipitated during freezing, so as to show excellent storage stability.
  • the solvent may be an organic solvent, and is preferably
  • the solvent may be used singularly or in combination.
  • the solvent and polyamide polymer may be used at a weight ratio of 20:80 to 90:10. Within the range, a sufficiently thick film can be obtained and good solubility and coating can be provided.
  • a method of making a photosensitive pattern by using a positive photosensitive resin composition is provided.
  • a method of making a photosensitive pattern using the positive photosensitive resin composition of the present invention includes: coating the above positive photosensitive resin composition on a supporting substrate and drying it to a resin composition layer; subjecting the resin composition layer to exposure; subjecting the exposed resin composition layer to development with an alkali development solution; and subjecting the developed resin composition layer to heating.
  • FIG. 1 is a view showing a process of making a pattern using a positive photosensitive resin composition. Hereinafter, the method is described in more detail referring to FIG. 1.
  • the subject 1 to be worked such as a semiconductor substrate is coated with a photosensitive resin composition to provide a photosensitive resin composition layer 2 (S1). Then, the photosensitive resin composition layer is exposed (S2) to generate a chemical change in the resin composition, and the dissolution rate of the exposed part is increased. Thereafter, it is developed with an alkali solution (S3) to provide a pattern.
  • the photosensitive resin composition layer formed with patterns When the photosensitive resin composition layer formed with patterns is heated, the pattern layer of the resin composition is cured to provide a photosensitive resin composition layer 6.
  • an electronic component for a semiconductor including the photosensitive resin layer obtained by using the positive photosensitive resin composition is applicable to a surface protective layer or an interlayer insulating layer. In addition, it is widely applicable to various fields requiring a positive pattern having high sensitivity and high resolution.
  • ⁇ Svnthesis Example 1> Synthesis of polvamide polymer 18.3g of 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane was added into a four-necked flask mounted with an agitator, a temperature controlling device, a nitrogen gas injector, and a condenser while nitrogen was flowing, and 28Og of N-methyl-2-pyrrolidone (NMP) was input thereto and dissolved.
  • NMP N-methyl-2-pyrrolidone
  • 4,4'-oxydibenzonyl chloride was dissolved in 142g of N-methyl-2-pyrrolidone (NMP) to provide a solution.
  • NMP N-methyl-2-pyrrolidone
  • the solution was slowly dripped therein for thirty minutes. For one hour after the dripping, the reaction was performed at 5° C, then the temperature was raised to room temperature and it was agitated for one hour. Subsequently, 1.5g of cyclohexyl carboxylchloride was input and agitated for one hour to complete the reaction.
  • a polyamide polymer represented by the following Chemical Formula 1-2 was synthesized in accordance with the same procedure as in Synthesis Example 1 , except that the 1.5g of cyclohexyl carboxylchloride was substituted with 1.5g of norbornane carboxylchloride.
  • the weight average molecular weight (Mw) of the polymer was 10K.
  • the precipitate was then filtered, sufficiently washed, and dried at 80 ° C under vacuum for 24 hours or more to synthesize a polyamide polymer represented by the following Chemical Formula 1 -3.
  • the polymer had a weight average molecular weight of 11 K. (Chemical Formula 1-3)
  • a polyamide polymer represented by the following Chemical Formula 1-4 was synthesized in accordance with the same procedure as in Synthesis Example 3, except that the 1.5 g of cyclohexyl carboxylchloride was substituted with 1.5g of norbornane carboxylchloride.
  • the polymer had a weight average molecular weight of 1OK.
  • a polyamide polymer represented by the following Chemical Formula 1-6 was synthesized in accordance with the same procedure as in Synthesis Example 5, except that the 1.5 g of cyclohexyl carboxylchloride was substituted with 1.5g of norbornane carboxylchloride.
  • the polymer had a weight average molecular weight of 1OK.
  • a polyamide polymer represented by the following Chemical Formula 1-7 was synthesized in accordance with the same procedure as in Synthesis Example 1 , except that the 1.5 g of cyclohexyl carboxylchloride was substituted with 1.5g of maleic acid anhydride.
  • the polymer had a weight average molecular weight of 1OK.
  • a polyamide polymer represented by the following Chemical Formula 1-8 was synthesized in accordance with the same procedure as in Synthesis Example 1 , except that the 1.5 g of cyclohexyl carboxylchloride was substituted with 1.5g of 5-norbornene-2,3-carboxylic acid anhydride.
  • the polymer had a weight average molecular weight of 11 K.
  • Each polyamide polymer synthesized from Synthesis Examples 1 to 8 was mixed with an esterified quinonediazide compound, a phenol group-included compound of 2,6-diacetoxy methyl-p-cresol, and a solvent of gamma-butyrolactone (GBL) in a composition ratio shown in the following Table 1 to provide a positive photosensitive resin composition.
  • GBL gamma-butyrolactone
  • 26a in Table 1 means a compound in which two of Qi to Q 3 in Chemical Formula 26 were represented by Chemical Formula 26-1 and the other one was hydrogen; and "26b” means a compound in which two of Qi to Q 3 in Chemical Formula 26 were represented by Chemical Formula 26-2 and the other one was hydrogen.
  • Each polyamide polymer obtained from Synthesis Examples 7 and 8 was mixed with an esterified quinonediazide compound, a phenol group-included compound, and a solvent in a composition ratio shown in the following Table 2 to provide a photosensitive resin composition.
  • the esterified quinonediazide compounds shown in the following Table 2 are the same as defined in Table 1.
  • Each positive photosensitive resin composition obtained from Examples 1 to 12 was coated on a silicone wafer and prebaked at 125 ° C for 120 seconds.
  • the silicone wafer coated with the photosensitive resin composition was exposed by a NikonMOc i-line stepper, which is exposure equipment, and was developed with a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for two minutes. It was immersed and washed in distilled water for one minute, and was measured using FE-SEM to determine CD (critical dimension).
  • TMAH tetramethylammonium hydroxide
  • the sensitivity was determined as an optimal exposure time by calculating the exposure time required for forming a 10 ⁇ m L/S pattern with a 1 to 1 line width after exposing and developing.
  • the resolution was determined as the minimum pattern size in the optimal exposure time.
  • Comparative Examples 5 to 8 in which positive photosensitive resin composition solutions according to Comparative Examples 1 to 4 were used had low transmission, so that the exposure energy was relatively higher than for those according to the examples, and the dissolution rate difference between the non-exposed part and the exposed part was 5 ⁇ m or more due to the carboxylic acid remaining in the terminal group.

Abstract

The present invention relates to a positive photosensitive resin composition that includes (A) a polyamide polymer, (B) an esterified quinonediazide compound, (C) a phenol group-included compound, and (D) a solvent. The positive photosensitive resin composition has excellent heat resistance and is capable of providing high sensitivity and high-resolution fine patterns.

Description

[DESCRIPTION] [Invention Title]
POSITIVE PHOTOSENSITIVE RESIN COMPOSITION [Technical Field] The present invention relates to a positive photosensitive resin composition. More particularly, the present invention relates to a positive photosensitive resin composition having excellent heat resistance and being capable of providing high sensitivity and high-resolution fine patterns. [Background Art] Recently, as semiconductor and liquid crystal display devices have tended to require higher integration, higher confidence, and higher density, researchers have actively undertaken studies on using organic materials having high purity and workability. Therefore, a surface protective layer and an interlayer insulating layer of a semiconductor device require a resin composition having excellent heat resistance and excellent electrical and mechanical characteristics. In addition, in order to satisfy the requirements of the surface protective layer and the interlayer insulating layer that are required to be more highly integrated, a resin composition that is capable of forming high resolution fine patterns has drawn attention. Forming patterns with a resin composition for a surface protective layer and an interlayer insulating layer having excellent heat resistance and excellent electrical and mechanical characteristics as well as being capable of forming fine high resolution patterns is a core technique, and it allows creation of an ultra-highly integrated semiconductor. The conventional positive photosensitive resin composition is prepared by adding esterified quinonediazide having photosensitivity to a polyamide polymer, or by covalent-bonding a polyamide polymer with quinonediazide. The general pattern forming process using the composition includes exposing the photosensitive resin composition to light having a certain wavelength with a patterning mask. In an exposed part, the quinonediazide compound is chemically changed to convert it to carboxylic acid. Subsequently, the exposed layer is contacted with a certain material (traditionally, an aqueous alkali developing solution). The part of the composition including the converted carboxylic acid increases solubility to the alkali developing solution, so as to be selectively developed thereby. The patterned layer is then heated to provide a cured pattern.
It is required to develop both a composition material having high heat resistance and excellent mechanical characteristics after the curing process and a patterning material having photo-characteristics of high resolution and high sensitivity, in view of the technique using the surface protective layer or the interlayer insulating layer. However, in order to improve the functions of the protective layer, it should be designed to provide a higher amount of aromatic compound, a higher polymer molecular weight, a higher degree of cross-linking, and lower fluidity, but in order to improve the photo-characteristics, it should be designed to provide a lower amount of aromatic compound, a lower polymer molecular weight, a lower degree of cross-linking, and higher fluidity, so it is not easy to develop a material satisfying the conflicting characteristics.
Particularly, because the fine pattern characteristics of the conventional polyamide are inversely proportional to the layer characteristics after curing, development of an improved photosensitive resin composition is limited.
In addition, while the soluble polyimide can improve the mechanical layer characteristics, it deteriorates the transmittance of the wavelength of exposure light due to the closed ring structure, so it finally decreases the resolution and sensitivity, and the characteristics for forming fine patterns are deteriorated.
As shown above, the conventional photosensitive resin composition still has problems of not satisfying the requirements of a finer pattern and improved mechanical characteristics needed for the improvement of the highly integrated semiconductor device. Accordingly, there is a need to develop a new form of photosensitive resin material that is required to overcome the limits of the conventional material. [DISCLOSURE] [Technical Problem] An exemplary embodiment of the present invention provides a positive photosensitive resin composition.
Another embodiment of the present invention provides a positive photosensitive resin having excellent heat resistance and being capable of forming a fine pattern having high sensitivity and high resolution. A further embodiment of the present invention provides a method of making a photosensitive pattern using the photosensitive resin composition.
Further embodiments of the present invention provide a photosensitive resin layer and a semiconductor electronic component that is produced using the positive photosensitive resin composition.
The embodiments of the present invention are not limited to the above technical purposes, and a person of ordinary skill in the art can understand other technical purposes. [Technical Solution]
According to one embodiment of the present invention, a positive photosensitive resin composition is provided that includes (A) a polyamide polymer having the following Formula 1 , (B) an esterified quinone diazide compound, (C) a phenol group-included compound, and (D) a solvent. [Chemical Formula 1]
Figure imgf000006_0001
In the above Formula 1 ,
Xi and X2 are the same or different and are independently a divalent to quadrivalent organic group, Yi and Y2 are the same or different and are independently a divalent to hexavalent organic group,
Ri and R2 are the same or different and are independently hydrogen or a C1 to C5 organic group,
Ei and E2 are the same or different and are independently hydrogen, or a moiety derived from one selected from the group consisting of monocarboxylic acid, and an active derivative thereof, provided that both Ei and E2 are not hydrogen, mi and m2 are the same or different and are independently 0 to 100, and mi+m2 ranges from 5 to 100.
According to another embodiment of the present invention, a method of making a photosensitive pattern is provided that includes coating the above positive photosensitive resin composition on a supporting substrate and drying it to a resin composition layer, subjecting the resin composition layer to exposure, subjecting the exposed resin composition layer to development with an alkali development solution, and subjecting the developed resin composition layer to heating. According to a further embodiment of the present invention, a semiconductor electronic component for a semiconductor including a photosensitive resin layer made using the positive photosensitive resin composition is provided.
Hereinafter, embodiments of the present invention will be described in detail.
[Advantageous Effects]
According to one embodiment of the present invention, the positive photosensitive resin composition includes one end or both ends of polyamide encapsulated by an alkyl group, an aryl group, an alicyclic group, or a heterocyclic group derived from a compound selected from the group consisting of monocarboxylic acid and activated derivatives, so as to maximize a dissolubility rate difference between the non-exposed part and the exposed part. Accordingly, when the pattern is formed with the photosensitive resin composition, the developing rate is increased at the exposed part, so that it is possible to form a high resolution pattern. After the curing process, the degree of close-ring and the degree of cross-linking are improved to provide a photosensitive resin layer having excellent film characteristics. [Description of the Drawings] FIG. 1 is a view showing a process of making a pattern using a positive photosensitive resin composition.
<Description of Reference Numerals Indicating Primary Elements in the Drawings>
1 : semiconductor device 2: photosensitive resin composition layer
3: exposed part of photosensitive resin composition layer 4: non-exposed part of photosensitive resin composition layer 5: patterned photosensitive resin composition layer after development 6: photosensitive resin composition layer after curing [Best Mode]
Exemplary embodiments of the present invention will hereinafter be described in detail. However, these embodiments are only exemplary and do not limit the present invention.
The photosensitive resin composition according to one embodiment of the present invention includes (A) a polyamide polymer represented by the following Formula 1, (B) an esterified quinone diazide compound, (C) a phenol group-included compound, and (D) a solvent.
As used herein, when specific definition is not provided, the term "substituted" refers to one substituted with at least a substituent including a halogen, an alkyl, an aryl, an alkoxy, an amino, or an alkenyl.
As used herein, when specific definition is not provided, the term "an alkyl" refers to a C1 to C30 alkyl, and preferably a C1 to C15 alkyl, the term "an aryl" refers to a C6 to C30 aryl, and preferably a C6 to C18 aryl, the term "an alkenyl" refers to a C2 to C30 alkenyl, and preferably a C2 to C15 alkenyl, the term "alkoxy" refers to a C1 to C30 alkoxy, and preferably a C1 to C15 alkoxy, and the term "alicyclic group" refers to a C3 to C40 cycloalkyl or a C3 to C40 cycloalkenyl, and preferably a C3 to C24 cycloalkyl or a C3 to C24 cycloalkenyl. As used herein, when specific definition is not provided, the terms
"divalent to quadrivalent organic group" and "divalent to hexavalent organic group" respectively refer to an organic group including 2 to 4 functional groups and an organic group including 2 to 6 functional groups. The functional groups are substituents excluding hydrogen. As used herein, when specific definition is not provided, the term
"heterocycle" refers to one selected from the group consisting of "heteroaryl", "heterocycloalkyl", "heterocycloalkenyl", and "heterocycloalkynyl".
As used herein, when specific definition is not provided, the term "hetero-compound" refers to a compound including at least one atom selected from the group consisting of N, O, P, and Si instead of carbon.
Each component will hereinafter be described in detail.
(A) Polvamide polymer
The polyamide polymer is represented by the following Formula 1. [Chemical Formula 1]
Figure imgf000010_0001
In the above Formula 1 ,
Xi and X2 are the same or different and are independently a divalent to quadrivalent organic group,
Yi and Y2 are the same or different and are independently a divalent to hexavalent organic group,
Ri and R2 are the same or different and are independently hydrogen or a C1 to C5 organic group, Ei and E2 are the same or different and are independently hydrogen, or a moiety derived from one selected from the group consisting of monocarboxylic acid and an active derivative thereof, provided that both Ei and E2 are not hydrogen, and preferably Ei and E2 are an alkyl, an aryl, an alicyclic group, or a heterocyclic group, mi and m2 are the same or different and are independently 0 to 100, and mi+m2 ranges from 5 to 100.
The polyamide polymer represented by the above Formula 1 is prepared as follows: a diamine monomer is reacted with an acid monomer selected from the group consisting of tetracarboxylic acid dianhydride, dicarboxylic acid anhydride, dicarboxylic acid, and active derivatives thereof to obtain a reaction product, and the reaction product is reacted with an end-capping monomer to convert an amine group of the reaction product to an amide group. The method of preparing the polyamide polymer is described in more detail.
The diamine monomer may be represented by X(NH2)2, wherein X is the same as Xi or X2 in Chemical Formula 1. The Xi and X2 of Chemical Formula 1 are derived from the diamine monomer. X may be represented by the following Formulae 2 to 7, but is not limited thereto.
[Chemical Formula 2]
Figure imgf000011_0001
[Chemical Formula 3]
Z3 Z4
A*
[Chemical Formula 4]
Figure imgf000011_0002
[Chemical Formula 5]
Figure imgf000011_0003
[Chemical Formula 6]
Figure imgf000012_0001
[Chemical Formula 7]
Figure imgf000012_0002
In the above Formulae 2 to 7,
Zi to Zi5 are the same or different, and are independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl, a hydroxy, a carboxylic acid group, and a thiol, and
Ai to A6 are the same or different, and are independently selected from the group consisting of CR3R4, S, O, SO2, CO, CONH, and a single bond, where
R3 and R4 are the same or different and are independently selected from the group consisting of hydrogen, or a substituted or unsubstituted alkyl, and preferably a fluoroalkyl.
The diamine monomer may include an aromatic diamine, an alicyclic diamine, and an aliphatic diamine.
Examples of the diamine monomer include benzidine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether,
1 ,4-bis(4-aminophenoxy)benzene, 4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone,
2,2-bis(4-amino-3-hydroxyphenyl)-1 ,1 ,1 ,3,3,3-hexafluoropropane, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylether) 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, para-phenylenediamine, meta-phenylenediamine,
1 ,5-naphthalenediamine, 2,6-naphthalenediamine cyclohexyldiamine, methylenebiscyclohexylamine, S.S'-diamino^^'-dihydroxybiphenyl,
3,3'-diamino-4,4'-dihydroxysulfone, 4,4'-diamino-3,3'-dihydroxyphenylsulfone, bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3l-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenylether1 1 ,4-diamino-2,5-dihydroxybenzene, and 1 ,3-diamino-2,4-dihydroxybenzene, but are not limited thereto. These diamine monomers can be used singularly or in combination.
The diamine monomer may preferably be selected from the group consisting of 4,4'-diaminodiphenylether, 4,4'-diaminodiphenyl methane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-diamino-4,4'-dihydroxysulfone, and mixtures thereof.
A silicon-included diamine monomer may be used along with the diamine monomer. The silicon-included diamine monomer increases adherence relative to a substrate. Examples of the silicon-included diamine monomer include bis(4-aminophenyl)dimethylsilane, bis(4-aminophenyl)tetramethylsiloxane, bis(p-aminophenyl)tetramethyldisiloxane, bis(gamma-aminopropyl)tetramethyldisiloxane, 1 ,4-bis-(gamma-aminopropyldimethylsilyl)benzene,
1 ,3-bis-(aminopropyl)tetramethyldisiloxane, and the like, but are not limited thereto. A preferable silicon-included diamine monomer includes bis(4-aminophenyl)tetramethylsiloxane, bis(p-aminophenyl)tetramethyldisiloxane, or a mixture thereof. In order to increase the adherence to the upper and lower layers, it is beneficial to use a copolymer of which a ratio of a silicon-containing diamine monomer to a diamine monomer not containing silicon is between 0.1 and 10 wt%. When the amount of silicon-included diamine monomer is within the range, the photo-characteristics and the layer characteristic are not deteriorated and the adherence is excellent.
The acid monomer that reacts with the diamine monomer may be selected from the group consisting of tetracarboxylic acid dianhydride, dicarboxylic acid anhydride, dicarboxylic acid, and an active derivative thereof. Yi and Y2 of Chemical Formula 1 are derived from the acid monomer. The tetracarboxylic acid dianhydride may be represented by the following Formula 8, but is not limited thereto. [Chemical Formula 8]
Figure imgf000015_0001
In the above Formula 8, Y is the same as Y1 or Y2 in Chemical Formula 1. The dicarboxylic acid monomer may be represented by Y(COOH)2, wherein Y is the same as Yi or Y2 in Chemical Formula 1.
The active derivative of the dicarboxylic acid monomer may be represented by Y(COFC)2, where Y is the same as Y1 or Y2 in Chemical Formula 1 , and K' is a moiety obtained by reacting Y(COOH)2 and a halide, or Y(COOH)2 and 1-hydroxy-1 ,2,3-benzotriazole. The following Formulae 9 to 16 may be derived from the acid monomer.
[Chemical Formula 9]
Figure imgf000015_0002
[Chemical Formula 10]
K3 K4
ΛΛ [Chemical Formula 11]
K5 ^"-B1\ K6
XJ \JL [Chemical Formula 12]
K7^ Jfi&
[Chemical Formula 13]
Figure imgf000016_0001
[Chemical Formula 14]
Figure imgf000016_0002
[Chemical Formula 15]
Figure imgf000016_0003
[Chemical Formula 16]
Figure imgf000016_0004
In the above Formulae 9 to 16,
Ki to K21 are the same or different, and are independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl, a hydroxy, a carboxylic acid group, a thiol, and COOR5, where R5 is hydrogen or a C1 to C5 alkyl, and
Bi to B6 are the same or different, and are independently selected from the group consisting of -CR6Rr-, -S-, -O-, -SO2-, -CO-, -CONH-, and a single bond, where R6 and R7 are the same or different and are independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl. The substituted alkyl preferably is a fluoroalkyl, and the unsubstituted alkyl is preferably a methyl.
The acid monomer may be tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, S.S'A^-biphenyltetracarboxylic acid dianhydride, 2,3,3',4-biphenyltetracarboxylic acid dianhydride,
3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, bis(3,4-dicarboxylphenyl)sulfone dianhydride,
1 ,1-bis-(2,3-dicarboxylphenyl)ethane dianhydride, bis(3,4-dicarboxylphenyl)ether dianhydride, and the like. The acid monomer may be a dicarboxylic acid active derivative such as a carbonyl halide derivative and an active ester derivative obtained by reacting an acid monomer and 1-hydroxy-1 ,2,3-benzotriazole. Specific examples of the active derivative include 4,4-oxydibenzonylchloride, phthalic dichloride, diphenyloxydicarboxylic acid chloride, bis(phenylcarboxylic acid chloride)sulfone, bis(phenylcarboxylic acid chloride)ether, bis(phenylcarboxylic acid chloride)phenone, phthalic carboxylic acid dichloride, diphenyloxydicarboxylate benzotriazole, and the like. Preferable acid monomers include 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, bis(3,4-dicarboxylphenyl)ether dianhydride, diphenyloxydicarboxylic acid chloride, phthalic carboxylic acid dichloride, and the like, but are not limited thereto.
The polyamide polymer represented by Chemical Formula 1 can be a copolymer in which two or more monomers are copolymerized within a range to not damage the photo-characteristics, the layer characteristic, and water-solubility of a homopolymer or polymer consisting of amide bond units. The copolymer may include various patterns, for example a random copolymer, a block copolymer, or a graft copolymer, but in one embodiment, it includes a random copolymer. In addition, the end-capping monomer reacting with the reaction product obtained by reacting an acid monomer with a diamine monomer may include a compound selected from the group consisting of monocarboxylic acid and active derivatives thereof.
The monocarboxylic acid may be any carboxylic acid, and particularly an alicyclic monocarboxylic acid such as cyclohexyl carboxylic acid, norbornane carboxylic acid, adamantyl carboxylic acid, isobornyl carboxylic acid, and norbornene carboxylic acid, or active derivatives thereof. The monocarboxylic acid can be used singularly or in combination.
The active derivative of the carboxylic acid includes cyclohexyl carboxyl chloride, norbornane carboxyl chloride, norbornene carboxyl chloride, adamantyl carboxylic acid chloride, isobornyl carboxylic acid chloride, 4-nadimido benzoyl chloride, cyclohexyl carboxylate benzotriazole, norbornene carboxylate benzotriazole, and the like.
The molecular weight of the polyamide polymer may be selected within a range so as to not damage the advantage of the present invention, but in one embodiment, the weight average molecular weight (Mw) ranges from 500 to 500,000, and in another embodiment, it ranges from 1000 to 50,000 in order to secure the effective dissolubility and coating property and to maximize the pattern-forming effect after patterning. When the weight average molecular weight is within the range, it is possible to provide sufficient physical properties and excellent solubility to the organic solvent, so as to make it convenient to handle.
[B] Esterified quinone diazide compound The esterified quinonediazide compound functions as a photo-active compound (PAC), and preferably includes a 1 ,2-benzoquinone diazide or 1 ,2-naphtoquinone diazide structure. These compounds are described in U.S. Patent Nos. 2,772,975, 2,797,213, and 3,669,658. The esterified quinonediazide compound may include the compound represented by the following Formulae 17 to 19, but is not limited thereto. [Chemical Formula 17]
Figure imgf000019_0001
[Chemical Formula 18]
Figure imgf000020_0001
[Chemical Formula 18-1]
Figure imgf000020_0002
[Chemical Formula 18-2]
Figure imgf000020_0003
[Chemical Formula 19]
Figure imgf000020_0004
In the above Formula 17 to 19, Gi to G4 are the same or different, and are independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl, and the alkyl is preferably a methyl, ni to n9 are the same or different, and are independently an integer ranging from 1 to 3, m3 is an integer of 0 to 3,
Di to D9 are the same or different, and are independently OQ, and
Q is hydrogen, or is represented by the above Formula 18-1 or 18-2.
The ratio that Q is hydrogen, that is to say, the substitution ratio of OH in an aromatic ring, ranges from 0 to 90mol%, and is preferably 30 to 80mol%.
Within the range, it can provide suitable photosensitivity and suitable photo-absorbance, so as to beneficially form patterns.
According to one embodiment, the esterified quinonediazide compound may be included at 1 to 50 parts by weight based on 100 parts by weight of the polyamide polymer, and in another embodiment, it ranges from 5 to 30 parts by weight. When the amount of the esterified quinonediazide compound is within the range, the pattern is well-formed without a residue from exposure, and it is possible to prevent a film thickness loss during development and to provide a good pattern. (C) Phenol group-included compound
The phenol group-included compound functions as a dissolution inhibitor to control a dissolution rate difference of an exposed part and a non-exposed part.
The phenol group-included compound includes 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, or 2,6-diacetoxymethyl-p-cresol, but is not limited thereto.
The phenol group-included compound may be represented by the following Formulae 20 to 25, but is not limited thereto. [Chemical Formula 20]
Figure imgf000022_0001
In the above Formula 20, R8 to Rio are the same or different, and are independently hydrogen, or a substituted or unsubstituted alkyl,
Rn to Ri5 are the same or different, and are independently selected from the group consisting of H, OH, and a substituted or unsubstituted alkyl, and the alkyl is preferably CH3, and nio is an integer of 1 to 5.
[Chemical Formula 21]
Figure imgf000022_0002
In the above Formula 21 ,
Ri6 to R21 are the same or different, and are independently selected from the group consisting of H, OH, and a substituted or unsubstituted alkyl,
A4 is CR1R" or a single bond, where R' and R" are the same or different, and is independently hydrogen, or a substituted or unsubstituted alkyl, and the alkyl is preferably CH3, and nii+ni2+ni3 and n-u+n-is+niβ are the same or different, and are independently integers of 5 or less. [Chemical Formula 22]
Figure imgf000023_0001
In the above Formula 22,
R22 to R24 are the same or different, and are independently hydrogen, or a substituted or unsubstituted alkyl, ni7, n-i8, and n2i are the same or different, and are independently integers of 1 to 5, and mg and n2o are the same or different, and are independently integers of 0 to 4.
[Chemical Formula 23]
Figure imgf000023_0002
In the above Formula 23,
R2δto R27 are the same or different, and are independently selected from the group consisting of hydrogen, OH, and a substituted or unsubstituted alkyl, and rtøto ri26 are the same or different, and are independently integers of 1 to 4, provided that n22+n24 and n23+n2β are independently integers of 5 or less.
[Chemical Formula 24]
Figure imgf000024_0001
In the above Formula 24,
R28 is a substituted or unsubstituted alkyl, and is preferably CH3,
R29 to R31 are the same or different, and are independently hydrogen, or a substituted or unsubstituted alkyl, n27, n29, and n3i are the same or different, and are independently integers of 1 to 5, and n28, n3o, and n32 are the same or different, and are independently integers of 0 to 4, provided that n27+n28, n29+n3o, and n3i+n32 are independently integers of 5 or less. [Chemical Formula 25]
Figure imgf000025_0001
In the above Formula 25,
R32, R33, and R34 are the same or different, and are independently a substituted or unsubstituted alkyl, and preferably CH3,
R35 to R38 are the same or different, and are independently hydrogen, or a substituted or unsubstituted alkyl, ri33, n35, and n39 are the same or different, and are independently integers of 1 to 5, ri34, ri36, and n38 are the same or different, and are independently integers of 0 to 4, and n37 is an integer of 1 to 4, provided that n33+n34, n35+n36, and n38+n39 are independently integers of 5 or less.
According to one embodiment, the phenol group-included compound is included at 0.1 to 30 parts by weight based on 100 parts by weight of a polyamide polymer. When the amount of the phenol group-included compound is within the range, it does not cause deterioration of sensitivity during the development, and it suitably increases the dissoluble rate of the non-exposed part to provide a good pattern. In addition, it is not precipitated during freezing, so as to show excellent storage stability. (D) Solvent
The solvent may be an organic solvent, and is preferably
N-methyl-2-pyrrolidone, gamma-butyrolactone, N,N-dimethylacetate, dimethylsulfoxide, diethyleneglycol dimethylether, diethyleneglycol diethylether, methyl lactate, ethyl lactate, methyl-1 ,3-butyleneglycolacetate, 1 ,3-butyleneglycol-3-monomethylether, diethyleneglycol dibutylether, propyleneglycol monomethylether, dipropyleneglycol monomethylether, propyleneglycolmonomethyletheracetate, methyl lactate, ethyl lactate, butyl lactate, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate, and the like, but is not limited thereto. The solvent may be used singularly or in combination.
The solvent and polyamide polymer may be used at a weight ratio of 20:80 to 90:10. Within the range, a sufficiently thick film can be obtained and good solubility and coating can be provided.
According to another embodiment, provided is a method of making a photosensitive pattern by using a positive photosensitive resin composition.
A method of making a photosensitive pattern using the positive photosensitive resin composition of the present invention includes: coating the above positive photosensitive resin composition on a supporting substrate and drying it to a resin composition layer; subjecting the resin composition layer to exposure; subjecting the exposed resin composition layer to development with an alkali development solution; and subjecting the developed resin composition layer to heating.
FIG. 1 is a view showing a process of making a pattern using a positive photosensitive resin composition. Hereinafter, the method is described in more detail referring to FIG. 1.
As shown in FIG. 1 , the subject 1 to be worked such as a semiconductor substrate is coated with a photosensitive resin composition to provide a photosensitive resin composition layer 2 (S1). Then, the photosensitive resin composition layer is exposed (S2) to generate a chemical change in the resin composition, and the dissolution rate of the exposed part is increased. Thereafter, it is developed with an alkali solution (S3) to provide a pattern.
During the exposure process (S2), when the photosensitive resin composition layer 2 is exposed by irradiating UV light of i-line and the like by using a photomask (not shown), the chemical change is generated by the photosensitive agent in the exposed part 3, but the chemical change is not generated in the non-exposed part 4. During the following process, when the exposed photosensitive resin composition layer is developed with an alkali aqueous solution (S3), the exposed part 3 that is chemically changed is removed to provide a pattern-formed photosensitive resin composition layer 5.
When the photosensitive resin composition layer formed with patterns is heated, the pattern layer of the resin composition is cured to provide a photosensitive resin composition layer 6. According to another embodiment of the present invention, provided is an electronic component for a semiconductor including the photosensitive resin layer obtained by using the positive photosensitive resin composition. The photosensitive resin layer 6 is applicable to a surface protective layer or an interlayer insulating layer. In addition, it is widely applicable to various fields requiring a positive pattern having high sensitivity and high resolution. [Mode for Invention]
The following examples illustrate the present invention in more detail. However, it is understood that the present invention is not limited by these examples.
<Svnthesis Example 1>: Synthesis of polvamide polymer 18.3g of 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane was added into a four-necked flask mounted with an agitator, a temperature controlling device, a nitrogen gas injector, and a condenser while nitrogen was flowing, and 28Og of N-methyl-2-pyrrolidone (NMP) was input thereto and dissolved.
When the solid was completely dissolved, 9.9g of pyridine was input into the solution. While the solution temperature was maintained at 5° C, 14.8g of
4,4'-oxydibenzonyl chloride was dissolved in 142g of N-methyl-2-pyrrolidone (NMP) to provide a solution. The solution was slowly dripped therein for thirty minutes. For one hour after the dripping, the reaction was performed at 5° C, then the temperature was raised to room temperature and it was agitated for one hour. Subsequently, 1.5g of cyclohexyl carboxylchloride was input and agitated for one hour to complete the reaction.
The reaction mixture was input in a solution of water/methanol = 10/1 (volume ratio) to generate a precipitate. The precipitate was filtrated and sufficiently washed with water, then dried at 80° C for 24 hours or more to synthesize a polyamide polymer represented by the following Chemical Formula 1-1. From the GPC results of the synthesized polymer, it was confirmed that the weight average molecular weight was 11 K. (Chemical Formula 1-1)
Figure imgf000029_0001
<Synthesis Example 2>: Synthesis of polvamide polymer
A polyamide polymer represented by the following Chemical Formula 1-2 was synthesized in accordance with the same procedure as in Synthesis Example 1 , except that the 1.5g of cyclohexyl carboxylchloride was substituted with 1.5g of norbornane carboxylchloride. The weight average molecular weight (Mw) of the polymer was 10K. (Chemical Formula 1-2)
Figure imgf000029_0002
<Synthesis Example 3>: Synthesis of polvamide polymer
17.4g of 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane and 0.86g of 1 ,3-bis-(aminopropyl)tetramethyldisiloxane were added into a four-necked flask mounted with an agitator, a temperature controlling device, a nitrogen gas injector, and a condenser while nitrogen was flowing, and 28Og of N-methyl-2-pyrrolidone (NMP) was input thereto and dissolved. When the solid was completely dissolved, 9.9g of pyridine was introduced into the solution, and a solution into which 13.3g of 4,4'-oxydibenzonyl chloride was introduced and dissolved in 142g of N-methyl-2-pyrrolidone (NMP) was slowly dripped thereto for thirty minutes while the temperature of the solution was maintained between 0 and 5° C. After dripping, it was reacted at a temperature of 5° C for one hour, and after raising the temperature to room temperature, the reaction was performed for one hour. 1.5 g of cyclohexyl carboxylchloride was introduced therein and agitated at room temperature for two hours, and then the reaction was completed.
The reaction mixture was introduced into a solution of water/methanol = 10/1 (volume ratio) to produced a precipitate. The precipitate was then filtered, sufficiently washed, and dried at 80° C under vacuum for 24 hours or more to synthesize a polyamide polymer represented by the following Chemical Formula 1 -3. The polymer had a weight average molecular weight of 11 K. (Chemical Formula 1-3)
Figure imgf000030_0001
<Svnthesis Example 4>: Synthesis of polyamide polymer
A polyamide polymer represented by the following Chemical Formula 1-4 was synthesized in accordance with the same procedure as in Synthesis Example 3, except that the 1.5 g of cyclohexyl carboxylchloride was substituted with 1.5g of norbornane carboxylchloride. The polymer had a weight average molecular weight of 1OK.
(Chemical Formula 1-4)
Figure imgf000031_0001
<Svnthesis Example 5>: Synthesis of polvamide polymer
18.3 g of 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane was added into a four-necked flask mounted with an agitator, a temperature controller, a nitrogen gas injector, and a condenser while nitrogen was flowing, and 280 g of N-methyl-2-pyrrolidone (NMP) was introduced and dissolved therein.
When the solid was completely dissolved, 9.9 g of pyridine was introduced into the solution, and a solution in which 11.8 g of 4,4'-oxydibenzonyl chloride and 2.5 g of phthaloyl chloride were dissolved into 142 g of N-methyl-2-pyrrolidone (NMP) was slowly dripped into the obtained solution for 30 minutes while the temperature was maintained at 5 ° C. After dripping, it was reacted at a temperature of 5° C for one hour and heated to room temperature. After agitating for one hour, 1.5 g of cyclohexyl carboxylchloride was introduced and agitated for one hour, and then the reaction was completed.
The reaction mixture was introduced into a solution of water/methanol =
10/1 (volume ratio) to produced a precipitate. Then the precipitate was filtered, sufficiently washed, and dried at 80° C under vacuum for 24 hours or more to synthesize a polyamide polymer represented by the following Chemical Formula 1 -5. The polymer had a weight average molecular weight of 11 K. (Chemical Formula 1-5)
Figure imgf000032_0001
<Svnthesis Example 6>: Synthesis of polvamide polymer
A polyamide polymer represented by the following Chemical Formula 1-6 was synthesized in accordance with the same procedure as in Synthesis Example 5, except that the 1.5 g of cyclohexyl carboxylchloride was substituted with 1.5g of norbornane carboxylchloride. The polymer had a weight average molecular weight of 1OK.
(Chemical Formula 1-6)
Figure imgf000032_0002
<Svnthesis Example 7>: Synthesis of polvamide polymer
A polyamide polymer represented by the following Chemical Formula 1-7 was synthesized in accordance with the same procedure as in Synthesis Example 1 , except that the 1.5 g of cyclohexyl carboxylchloride was substituted with 1.5g of maleic acid anhydride. The polymer had a weight average molecular weight of 1OK. (Chemical Formula 1-7)
Figure imgf000033_0001
<Svnthesis Example 8>: Synthesis of polvamide polymer
A polyamide polymer represented by the following Chemical Formula 1-8 was synthesized in accordance with the same procedure as in Synthesis Example 1 , except that the 1.5 g of cyclohexyl carboxylchloride was substituted with 1.5g of 5-norbornene-2,3-carboxylic acid anhydride. The polymer had a weight average molecular weight of 11 K.
(Chemical Formula 1-8)
Figure imgf000033_0002
<Examples 1 to 12>: Synthesis of Photosensitive Resin Composition
Each polyamide polymer synthesized from Synthesis Examples 1 to 8 was mixed with an esterified quinonediazide compound, a phenol group-included compound of 2,6-diacetoxy methyl-p-cresol, and a solvent of gamma-butyrolactone (GBL) in a composition ratio shown in the following Table 1 to provide a positive photosensitive resin composition.
"26a" in Table 1 means a compound in which two of Qi to Q3 in Chemical Formula 26 were represented by Chemical Formula 26-1 and the other one was hydrogen; and "26b" means a compound in which two of Qi to Q3 in Chemical Formula 26 were represented by Chemical Formula 26-2 and the other one was hydrogen.
[Chemical Formula 26]
[Chemical Formula 26-1]
Figure imgf000034_0002
[Chemical Formula 26-2]
Figure imgf000034_0003
Table 1
Figure imgf000035_0001
Figure imgf000036_0001
<Comparative Examples 1 to 4>: Synthesis of Photosensitive Resin Composition
Each polyamide polymer obtained from Synthesis Examples 7 and 8 was mixed with an esterified quinonediazide compound, a phenol group-included compound, and a solvent in a composition ratio shown in the following Table 2 to provide a photosensitive resin composition. The esterified quinonediazide compounds shown in the following Table 2 are the same as defined in Table 1.
Table 2
Figure imgf000037_0001
<Examples 13 to 24>: Lithography Test
Each of the photosensitive resin compositions obtained from Examples 1 to 12 was subjected to a lithography test, and the results were set for Examples 13 to 24 and are shown in Table 3.
Each positive photosensitive resin composition obtained from Examples 1 to 12 was coated on a silicone wafer and prebaked at 125° C for 120 seconds.
The silicone wafer coated with the photosensitive resin composition was exposed by a NikonMOc i-line stepper, which is exposure equipment, and was developed with a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for two minutes. It was immersed and washed in distilled water for one minute, and was measured using FE-SEM to determine CD (critical dimension).
Furthermore, the sensitivity was determined as an optimal exposure time by calculating the exposure time required for forming a 10 μ m L/S pattern with a 1 to 1 line width after exposing and developing. The resolution was determined as the minimum pattern size in the optimal exposure time.
After forming the pattern, it was heated under a nitrogen atmosphere at 150° C for 30 minutes, and the temperature was raised to 350° C for one hour to provide a cured film.
Table 3
Figure imgf000039_0001
Referring to Table 3, it is confirmed that all resolutions had excellent values of 3 μ m or less. In addition, it is confirmed that the exposure energy values showed excellent photo-characteristics of 400 mJ/cm2 or less. That is, it is estimated that the terminal group of the polyamide polymer was not derived from anhydride, but it was substituted to an alkyl group, an alicyclic group, or an aryl group, so that the transmission was increased while the dissolution rate difference between the non-exposed part and the exposed part was maximized. <Comparative Example 5 to 8>: Lithography Test
The same lithography test was carried out in accordance with the same procedure as in Example 13, except that the photosensitive resin composition was obtained from each of Comparative Examples 1 to 4. The results were set for Comparative Examples 5 to 8 and are shown in the following Table 4.
Table 4
Figure imgf000040_0001
As shown in Table 4, Comparative Examples 5 to 8 in which positive photosensitive resin composition solutions according to Comparative Examples 1 to 4 were used had low transmission, so that the exposure energy was relatively higher than for those according to the examples, and the dissolution rate difference between the non-exposed part and the exposed part was 5 μ m or more due to the carboxylic acid remaining in the terminal group.
In addition, although it described with an L/S (line and space) pattern in the examples, the present invention is not limited thereto, but it may be applied to all various patterns such as a hole pattern.
While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

[CLAIMS] [Claim 1]
A positive photosensitive resin composition comprising: (A) a polyamide polymer represented by the following Formula 1 ; (B) an esterified quinonediazide compound;
(C) a phenol group-included compound; and
(D) a solvent: [Chemical Formula 1]
Figure imgf000042_0001
wherein in the above Formula 1 ,
Xi and X2 are the same or different and are independently a divalent to quadrivalent organic group,
Yi and Y2 are the same or different and are independently a divalent to hexavalent organic group, Ri and R2 are the same or different and are independently hydrogen or a
C1 to C5 organic group,
Ei and E2 are the same or different and are independently hydrogen, or a moiety derived from one selected from the group consisting of monocarboxylic acid and an active derivative thereof, provided that both Ei and E2 are not hydrogen, mi and m2 are the same or different and are independently 0 to 100, and mi+m2 ranges from 5 to 100.
[Claim 2]
The photosensitive a resin composition of claim 1 , wherein the esterified quinonediazide compound is includes in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polyamide polymer, the phenol group-included compound is included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the polyamide polymer, and the solvent and the polyamide polymer are included at a weight ratio of 20:80 to 90:10.
[Claim 3]
The positive photosensitive resin composition of claim 1 , wherein the polyamide is prepared by a method comprising: reacting a diamine monomer with an acid monomer selected from the group consisting of tetracarboxylic acid dianhydride, dicarboxylic acid anhydride, dicarboxylic acid, and active derivatives thereof to obtain a reaction product; and reacting the reaction product with an end-capping monomer to convert an amine group of the reaction product to an amide group.
[Claim 4]
The positive photosensitive resin composition of claim 3, wherein the diamine monomer is represented by X(NH2)2, wherein X is the same as Xi or X2 in Chemical Formula 1.
[Claim 5]
The positive photosensitive resin composition of claim 3, wherein the diamine monomer comprises a non-silicon diamine monomer and is represented by X(NH2)2, wherein X is the same as Xi or X2 in Chemical Formula 1, and a silicon-included diamine monomer.
[Claim 6]
The positive photosensitive resin composition of claim 3, wherein the acid monomer is a dicarboxylic acid monomer represented by Y(COOH)2, wherein Y is the same as Yi or Y2 in Chemical Formula 1.
[Claim 7]
The positive photosensitive resin composition of claim 3, wherein the acid monomer is represented by Y(COK')2, wherein Y is the same as Yi or Y2 in Chemical Formula 1 , and K1 is a moiety obtained by reacting Y(COOH)2 and a halide, or Y(COOH)2 and 1-hydroxy-1 ,2,3-benzotriazole.
[Claim 8] The positive photosensitive resin composition of claim 3, wherein the acid monomer is tetracarboxylic acid anhydride represented by the following Formula 8: [Chemical Formula 8]
Figure imgf000045_0001
wherein in the above Formula 8, Y is the same as Yi or Y2 of Chemical Formula 1.
[Claim 9]
A method of making a photosensitive pattern, comprising: coating the positive photosensitive resin according to one of claims 1 to 8 composition on a supporting substrate and drying it to a resin composition layer; subjecting the resin composition layer to exposure; subjecting the exposed resin composition layer to development with an alkali development solution; and subjecting the developed resin composition layer to heating.
[Claim 10]
A photosensitive resin layer made using the positive photosensitive resin composition according to one of claims 1 to 8.
[Claim 11 ] An electronic component for a semiconductor, comprising a photosensitive resin layer according to claim 10.
PCT/KR2008/007907 2008-10-07 2008-12-31 Positive photosensitive resin composition WO2010041795A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07281441A (en) * 1994-04-06 1995-10-27 Sumitomo Bakelite Co Ltd Positive type photosensitive resin composition
US5858584A (en) * 1996-05-27 1999-01-12 Hitachi, Ltd. Positive photosensitive resin composition and electronic apparatus using the same
US20020090564A1 (en) * 2000-11-27 2002-07-11 Mitsuhito Suwa Composition of positive photosensitive resin precursor, and display device thereof
WO2008020573A1 (en) * 2006-08-15 2008-02-21 Asahi Kasei Emd Corporation Positive photosensitive resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07281441A (en) * 1994-04-06 1995-10-27 Sumitomo Bakelite Co Ltd Positive type photosensitive resin composition
US5858584A (en) * 1996-05-27 1999-01-12 Hitachi, Ltd. Positive photosensitive resin composition and electronic apparatus using the same
US20020090564A1 (en) * 2000-11-27 2002-07-11 Mitsuhito Suwa Composition of positive photosensitive resin precursor, and display device thereof
WO2008020573A1 (en) * 2006-08-15 2008-02-21 Asahi Kasei Emd Corporation Positive photosensitive resin composition

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