TW201128324A - Composition for forming protective layer on photoresist pattern - Google Patents

Abstract

A composition which can wash a photoresist pattern and form a protective layer by heating after washing during double exposure patterning process, and a method for forming a fine pattern in a semiconductor device using the same are disclosed. The composition for washing a photoresist pattern and forming a protective layer, comprises one or more crosslinking agent selected from the group consisting of compounds represented by the Formulas 1 to 3 stated in the specification; and a solvent. In Formulas 1 to 3, R1 is a chain type, branch type or ring type hydrocarbon group of 1 to 15 carbon atoms containing 0 to 10 of hetero atoms, R2 is a chain type, branch type or ring type hydrocarbon group of 1 to 10 carbon atoms, R3 may not exist, or is a chain type, branch type or ring type hydrocarbon group of 1 to 10 carbon atoms containing 0 to 5 of hetero atoms, R4 and R5 are independently a hydrogen atom or a chain type, branch type or ring type hydrocarbon group of 1 to 6 carbon atoms containing 0 to 5 of hetero atoms, R4 and R5 can be connected to each other to form a ring, and n is an integer of 2 to 6, p is an integer of 10 to 250, and q is an integer of 1 to 140.

Description

201128324 VI. INSTRUCTIONS: This application is based on the Korean Patent Applicant's case number 1〇-20〇9-〇1() 2271, which was submitted on January 27, 2009. All of this Korean: The disclosure of the application is incorporated herein by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for cleaning a photoresist pattern t and forming a protective layer, and more particularly to a composition which can clean a photoresist pattern and clean it in a double exposure patterning process. Thereafter, a protective layer is formed by heating, and a method of forming a fine pattern in a semiconductor device using the composition. [Prior Art] In processing a semiconductor wafer or display glass to a semiconductor wafer or display element, it is necessary to establish a designed circuit on the semiconductor wafer or the display glass by a photolithography process. As the integration of circuits increases, higher analytical patterning is required in the photolithography process. In order to obtain the high-resolution pattern, a method using, for example, using a shorter wavelength (λ) light as an exposure source, and filling a liquid having a refractive index higher than air between the photoresist layer and the lens such that the numerical aperture (ΝΑ) is larger than 1, and by introducing an additional process, the process parameter b is less than 〇·3. In detail, KrF laser light having a wavelength of 248 nm (nanometer) is used as an exposure source to fabricate a semiconductor device having a pattern resolution of 9 Å to 2 Å, and an ArF laser light having a wavelength of 193 nm is used as an exposure source. A semiconductor device having a pattern resolution of 6 〇 to 9 〇 nm is produced. In order to obtain 4 201128324 ultra-fine pattern semiconductor device with a resolution of 40 to 60 nm, a dip: lithography process is used to make the numerical aperture (NA) greater than i. In this method, the exposure is performed on the light coated on the wafer. Between the resist layer and the projection lens, and fill the refractive index of the deionized water (10) in U4, without using the air of the fold (four) 1. The technique for fabricating a device having a resolution of 30 nm in the study is a double-patterning process, which is a modification of a conventional single photolithography process. The double patterning process is performed by repeating two conventional single photolithography processes: a process parameter kd of 0.25 or less to form an ultrafine pattern. As another method for reducing the process parameter 1^, there is a double exposure patterning process and a spacer patterning technique (SPT). "The double exposure patterning method (process) comprises the steps of: coating a first photoresist layer on a semiconductor substrate on which a (four) layer has been formed, and re-forming an anti-reflective coating layer; The first photoresist layer is selectively exposed and developed using an exposure mask to form a first photoresist pattern " see a photoresist pattern formed by cleaning; forming a protection on the first photoresist pattern Forming a second photoresist layer thereon; and selectively exposing and developing the second photoresist layer using an exposure mask to form a second photoresist pattern between the first photoresist patterns. In the method, before the second photoresist pattern is formed, a protective layer is formed on the first photoresist layer to protect the first photoresist pattern. According to the convention, the protective layer is a (four) liquid coating method or a self-hardening anti-surname agent. ^成. Solution coating side & 'Because of the solution involved in coating and baking the protective layer, removing the residual protective layer and hard baking' has many shortcomings of the 201128324 complex process due to many steps. The disadvantage of the method of hardening (4) is that it must be made The self-hardening resist is used as the composition to form the first photoresist pattern, and at the same time, only the protective layer of the first photoresist pattern can be formed by baking. Accordingly, the object of the present invention is to provide a use and formation. a protective layer composition which is applied to a photoresist pattern which has been cleaned by a cleaning method. The method of forming a fine pattern in a semiconductor device by heating in a photoresist pattern is performed in order to achieve such a pattern. OBJECTIVE: The present invention is directed to a combination of only one of the ingredients for cleaning the photoresist pattern and forming the protective layer. #/+1# The following formula 1 to formula 3 Take 4 [formula i] top 'and solvent. [Formula 2] ^ΝΗ2ΐη [Formula 3]

D. In the formulas 1 to 3, νη2 1 is a chain shape of 0 carbon atoms, 10 to 15 filaments of a hetero atom, and 1 to 15 chain or cyclic hydrocarbon groups D i ' I is 1 to 10 carbon atoms 6 201128324 = chain, branched chain or ring-shaped nicotine, R3 may be a hetero atom with a chain shape of 1 to 10 carbon atoms, a sub-group containing an anthracene hydrocarbon group, and an independent branch of R5 and a ring to 6 carbon atoms. Chain shape, branch original:: two; to 5 impurities to form a ring, n is 2 6 5 % hydrocarbon group 'R' R5 can be ..., to an integer of 6, d is 1 nz: number, q An integer from 1 to 140. The entire invention of 0 to 25 并 is provided in a semi-method comprising the steps of: forming a square semiconductor substrate on which a fine pattern is formed in a germanium device; by forming a rich layer in the present a first photoresist pattern; the first photoresist pattern is immersed in the composition for the pattern of the sound retardation pattern by using a stalking stalk, a first, and a smock to form a β ^ ^ - the photoresist pattern 'by the cleaned first - light m vine layer' by first resistance pattern at 150 to 20 (TC heating (hardened for baking) to form a protective layer; in 1 shape & @, ... eight Forming a second photoresist layer on the tempering layer; and forming a second resist layer according to the present invention by exposing and developing the first precursor layer to a resist pattern. The utility model can be used for simultaneously cleaning the photoresist pattern and forming the protective layer. That is, in the process of forming the first pattern and using the composition to clean the pattern, only the heating can be used. The (baking) process forms a protective layer on the pattern. Therefore, the composition according to the present invention is used because The process of forming the protective layer of the invention in April and the alpha species can be simplified and economic benefits can be obtained by reducing the number of processes. Therefore, it is useful to form a fine pattern of a semiconductor device by using a double exposure patterning method. 7 201128324 Referring to the following detailed description, the machine can be understood for the present invention and many of the advantages. 'The composition for producing ice on the π 冼 first resistance pattern and forming the protective layer according to the present invention can be used simultaneously After forming the donut-solid α-resistance pattern, the photoresist pattern is cleaned and a cross-linking layer comprising a compound selected from the group consisting of the following formulas 1 5 ^ i to 3 is formed; and a solvent. Formula 1] M~NH2ln is 1 to 15 in the formula l'Ri, 2 anti-atoms, preferably 2 to 10 carbon atoms in a chain shape, a branched chain or a cyclic hydrocarbon, preferably 0 to 5 heteroatomic atoms, 3 heteroatoms, such as oxygen atom (8), nitrogen 2, 3 heteroatoms, hetero atom, (F), 1 atom (S;; equiatomic (8), gas atom (6)), an integer of fluorocarbon. An integer of 2 to 6 is preferably 2 to * 2] ~fR2 7 sub, :: 2?: two 1 to 1 The carbon atom ' is preferably 1 to 6 carbon atoms or alkyl groups or branched, branched or cyclic hydrocarbon groups (for example, preferably...=::, may be absent or ... More chain or ring-shaped nicotine (for example, two to three strands of a helium atom, branch 0 to 5 hetero atom M & base, extended aryl ' or several bases), containing sub (8), air shoulder (8) ? 3 heteroatoms 'heteroatoms such as oxogen 莩. L and Μ蜀 are hydrogen atoms, or to 6 201128324 carbon atoms, for example, 1 to 3 carbon atoms of a chain, branched chain or cyclic hydrocarbon group Containing 0 to 5 heteroatoms, for example, to 3 heteroatoms, heteroatoms such as an oxygen atom (〇), a nitrogen atom (N), and the like. L and L may be bonded to each other to form a ring, and p is an integer of from 10 to 250, preferably an integer of from 1 Å to 15 Å. Conventionally, the weight average molecular weight of the compound represented by Formula 2 (, from 700 to 40, 〇〇〇' is preferably from 1, 至 to 1 〇.

Η 2 ΝΓ — V, which is represented by Formula 3, q is an integer of 1 to 140, preferably an integer of 5 to 1 。. The compound represented by Formula 3 by convention has a weight average molecular weight of from 500 to 75,000, preferably from [, 〇〇〇 to 1〇 〇〇〇. Wherein R 4 and R s may be an aromatic or aliphatic hydrocarbon group, and if desired, may be substituted with a substituent 'substituted 丨 〜 η η 丞 丞 carboxy ( _C00H), carbonyl (c = 〇), amine ( -NH2), via "πιιλ L-based (-ΟΗ), halogen atom (F, CI, etc.), etc., and Q, which are randomly selected to represent the type of polymeric sound, and can be selected according to the monomer structure and resist. Examples of the agent, a compound containing two or more first-order amine groups (cross) include:

9 201128324 h2n, if , nh2

Η

H2N H

The compound represented by Equation 2 of H2N (crosslinking agent, a water-soluble polymer containing a nitrogen atom) contains a nitrogen atom in the form of an amine group, a carbazolyl group, a guanamine group or the like, preferably an amine group. Water soluble polymer. Examples of the compound represented by Formula 2 include the compounds represented by the following Formulas 2a to 2d. [Formula 2a] Λ [Formula 2b] 10 201128324

[Formula 2c]

Η

〇a= P

[Formula 2d] Η

The formulas 2a to 2d are the same as the definition of the formula 2. '♦ 赞 使 取 取 , 小 , , , , 稽 稽 稽 稽 稽 稽 兴 兴 兴 兴 兴 兴 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 双重 双重 双重 双重 双重 双重 双重 双重In the step of washing and adding, (s, baking), on the surface of the first face I first P pattern, using the oxygen substituent of the crosslinking agent photosensitive polymer 'such as vinegar γ=) , (Q'), etc. (preferably, a deprotection knife of a photosensitive polymer, such as a carboxyl group (_c〇〇H), a 〇i 〇μ sheath, a poly(), etc.) Forming a L-form parental agent (Formula 2 or 3 represents 5 to 5, 0 〇〇 i ± initial) may include ln ^ preferably from 10 to 2,000 nitrogen atoms, from 10 to 500 nitrogen atoms, See the original thousand, for example, 'to maximize the effect of forming a protective layer. The amount of the cross-linking agent, the total amount of the composition of the material dew 4 / is used for cleaning the photoresist pattern and forming a protective layer %. It is preferred if the crosslinking agent is from 1% by weight to 1% by weight. .5 to 5 is difficult. If the crosslinking agent:: °·1% by weight of 'forming a protective layer may be and economically undesired: 10% by weight, there is no particular advantage, 201128324 The solvent used in the present invention is used for cleaning formation The residue of the photoresist layer remaining on the photoresist pattern after the photoresist pattern. As the solvent, a solvent used in a conventional cleaning solution can be used. For example, deionized water (DIW), ozone water, lower alcohols having less than 5 carbon atoms, organic solvents such as glycols and mixtures thereof, preferably deionized water (DIW), ozone water, methanol, ethanol, and different Propanol, acetone, dimethyl hydrazine and mixtures thereof. The amount of the solvent is from 90 to 99.9% by weight, preferably from 95 to 99% by weight, based on the composition for cleaning the photoresist pattern and forming the protective layer. If the amount of the solvent is less than 90% by weight, the effect of cleaning the photoresist pattern may be lowered. If the amount of the solvent is more than 99.9% by weight, the amount of the crosslinking agent is relatively reduced, so that it may be difficult to form a protective layer. The group 1 for cleaning the photoresist pattern and forming the protective layer according to the present invention further includes an additive for increasing the effect of cleaning the photoresist pattern, for example; a surfactant, a pH controlling agent, and tetrakis ammonium hydroxide (τμαη) )Wait. The surfactant is added to mix the composition for cleaning the photoresist pattern and to improve the cleaning effect. As a 7=:agent', a conventional surfactant can be used without limitation, for example, an alkanesulfonic acid name such as a hydrazinium imine, a fluorene acid derivative, or a nitrogen compound and a acid derivative. And/or a test compound of a fluoro correcting acid derivative. ^ When the surfactant is used, the amount of the surfactant is 001 to 1% by weight, preferably 〇%, relative to the crosslinking agent and the mJ 100 replacement portion. ¥ Bo· w υ· 0 3 泫 The amount of surfactant (solid content) is less than 0 01% by weight, possible. The method completely removes the resist residue. If the amount of surfactant L 1 is heavy! The viscosity of the %' composition will increase, and the load of the composition of the present invention will increase, so that the composition of the present invention may not play a fundamental role as a solution for cleaning the photoresist pattern. Compared with the conventional double exposure patterning process, the method for forming a fine pattern in a +conductor device of the present invention has a cleaning photoresist pattern. This step utilizes the inventor of the present invention and has formation protection. The step 'which replaces the heating (baking) photoresist pattern. For example, the method of the present invention comprises the steps of: (1) forming a first photoresist layer on a semiconductor substrate on which the (four) layer is formed; (" using an exposure mask having a line and space (L/S) pattern, using the first a photoresist layer selective #•... 疋悍r is exposed and developed to form a first photoresist pattern; (iii) is immersed in a composition of a crosslinking agent and a solvent represented by Formula 1 of the present invention. And cleaning the first pattern of the first resistance, (iv) heating the first photoresist pattern of the month by the 芏wo c (hardening drying ' is preferably 16G to 18Gt to form a protective layer; (7) Forming a first photoresist layer thereon; and (vi)#using #; using an exposure mask, by selectively exposing and developing the second photoresist layer to be in the first resistance pattern. (4) Patterning Forming a second light to heat (harden and bake) process 'encoding oxygen substituents of the photosensitive polymer on the surface of the first photoresist pattern such as vine (Lu), meimei (4), bond group (_〇_), etc. (preferably, a deprotecting knife of a photosensitive polymer such as a county (_(10)Η), (4) (a), etc.), and an amine group of a crosslinking agent, by The cleaning of the first photoresist pattern is heated to bond and crosslink hard to form a protective layer on the surface of the first photoresist pattern. If the heating temperature of the addition-hardening block baking process is 150t, the protective layer may not be formed on the photoresist pattern, and if the heating (hardening for baking) process is 13 201128324, the heating temperature is higher than 2〇〇〇e, # The first photoresist pattern may melt. As the photosensitive polymer for forming the first and second photoresist compositions which can be used in conventional photoresists, the light X 4 includes the following formula 4 to represent a photoacid generator for use in the production of a compound ( A photo-resist composition such as a base quencher), an alkalization of a metamorphic acid diffusion, a stimulant, and the like. [Formula 4]

R R R ^CH2-^cH2-^CH2-|f-0==== 0= 〇==

0 I X

0 IY ; Formula 4 R is independently a hydrogen atom, or a methyl group, [γ ground, a bond containing 0 to 20 Μ 1 independent branch bond or a cyclic aromatic 25 carbon atom, a clothing aroma or fat A hydrocarbon group. More than 10 heteroatoms such as oxygen atoms (^ have a chain of 0 atoms, a branched chain with 1 to 20 carbons of the nitrogen atom (8) (four), or contain == two r... is a base. _ base' or contains... A hetero atomic oxime, a branched chain or a cyclic aromatic or aliphatic hydrocarbon group \a=C each represents 11〇1% with respect to the single I, complex unit constituting the polymer. 3 is 10 to 75 1〇 /... (Repeat early) The weight _... is preferably: 2々 to 7〇m〇1%, c is 1〇 to more than 15 to 5". 1%, more preferably 2. to 3". 1%. If the _ is repeated from the above range, the properties of the photoresist layer may be degraded, and it is difficult to 2 14 201128324 photoresist layer' and the pattern contrast may be lowered. As usual, the weight average molecular weight of the photosensitive polymer (Mw The preferred embodiment is provided for a better understanding of the present invention, in the range of 2, 000 to 20, 〇〇〇, preferably 3, 〇〇〇 to 12, 000 。. However, the present invention is not limited to the embodiments. [Examples 1 to 19] of the cover layer are prepared for cleaning the photoresist pattern and forming the composition for cleaning. The crosslinking agent, the surfactant, and the solvent according to Table 1 below are mixed. And the mixture was stirred for 4 hours and filtered to obtain a composition in which the resist pattern was uniformly mixed and a protective layer was formed.

15g sulfonyl quinone imine 0. 15g sulfonyl quinone imine 0. 15g [Table 11 Interfacial activity] 15克 sulfonyl quinone imine 0. 15g sulfonyl quinone imine 0. 15g

Deionized water 99. 5g Deionized water deionized water 99. 5g —~~~~~— Deionized water 99. 5g 15 201128324 Deionized water Example 9 Sulfonyl quinone imine 0. 5克为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为千 去 实施 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 5g 脱水。 99g 5w Mw = 5g Mw = 5g Mw = 5g Mw = 9g Mw = 5g Mw = 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。克 去 70 15 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 5g

[Examples 20 to 40] Forming a fine pattern of a semiconductor device, and its test A. Forming a first photoresist pattern 16 201128324 After the first photoresist composition according to Table 2 below was stirred at room temperature for * hour, 'filtering the combination The material is coated on the wafer and softly baked for n seconds at n 〇〇c. Then, an exposure mask having a line and space (L/s) pattern and an exposure of 1 9 ArF exposure (ASML 1200 Β) were used, and at 11 〇. After the flood, the roast and the. It was developed with 2.38 wt% TMAH (tetramethylammonium hydroxide) aqueous solution to form a pattern of 50 nm L/S 1 :3 pitch. B. Cleaning the first photoresist pattern and forming a protective layer. After cleaning the first photoresist pattern by dipping in the composition manufactured in Examples 1 to 19 for 3 minutes, the washed pattern was used. A coating and baking apparatus (device name: track Baker) manufactured by electron Ltd. (TEL) was heated at 180 ° C to form a protective layer on the surface of the first photoresist pattern. C. Forming a second photoresist pattern. After the second photoresist composition according to Table 2 below was mixed for 4 hours at room temperature, the second photoresist composition was filtered and coated on a protective layer, and softened at 11 〇艽. Bake for 60 seconds. Then, it was exposed to light of a wavelength of 193 nm using ASML 120 〇B, and baked at 110 ° C for 60 seconds. It was then developed with 2.38 wt% TMAH (tetramethylphosphonium hydroxide) aqueous solution to form a first photoresist pattern of 5 〇 nin L/s 1 : 3 pitch. As a result, the first photoresist pattern and the second photoresist pattern were in a pattern of 50 nm L/S 1 :1 pitch (Examples 2 to 4). Fig. i is a scanning electron microscope (SEM) photograph of a fine pattern (a pattern of 5 〇 nm L/s 1 ··^ pitch) formed in Example 29 of the present invention. 201128324 [Table 2] (A-l

Ho (Mw = 3, 000 〜1 2, 000 )) Photosensitive Polymer Photoacid Generator Quencher Solvent First Photoresist Composition A-1-1 5g Perfluorobutanesulfonic Acid Triphenylsulfonium Salt (Triphenylsulfonium nonaflate) 〇.2g trioctylamine 〇.〇2g propylene glycol monomethyl ether acetate (PGMEA) l〇〇g second photoresist composition [schematic diagram] FIG. 1 shows an embodiment of the present invention SEM (Scanning Electron Microscope) photograph of the fine pattern formed by 29. [Main component symbol description] None 18

Claims (1)

201128324 VII. Scope of Application for Patention·· 1 · A composition for cleaning a flower comprising: a redundant pattern and a protective layer, selected from the group consisting of the following formulas 1 to 3; and a solvent: a group of non-compounds One of them is [Formula 1] [Formula 2] RiH-NH2 j Tp [Formula 3] wherein, in Formulas 1 to 3, t is a chain of human _~N~NH2 carbon atoms, and octagonal to 1 〇 A 1- to amino chain of a hetero atom, a branched chain-shaped hydrocarbon group, and L is from 1 to 10 to 5 heteroatoms! 5 坆, R3 may be absent or contain a smoky group, ..., independently = =, ..., a chain of 1 to 6 carbon atoms, a subordination: 3 with 0 to 5 heterogenes may be mutually Linked to form a ring, and ...:: an integer of a two-ring hydrocarbon group, ... to an integer of 0, an integer '.... to 2 成 into 4 layers, please use the first item for cleaning the photoresist pattern and The composition of the wind protection layer, which is a group of the formula ▲ 固素 and Kaiyi: /, the parent agent, selected from the following 19 201128324 ,νη2 Η2ίΤ !ί η η2ν η, ν^^ν^^ν^^ΝΗ2 Η Η2ν 八Η2ν^^/^/^νη2, Η2Ν 八, Η2Ν·^^^^^^2, >, and mixtures thereof. 3. The composition for cleaning a photoresist pattern and forming a protective layer according to claim 1, wherein the crosslinking agent represented by Formula 2 is selected from the group consisting of compounds represented by the following Formulas 2a to 2d: [Formula 2a] h, N, h [Formula 2b] 20 201128324 [Formula 2c] P Η [Formula 2d] wherein, in the formulas 2a to 2d, p is the same as the fixed lid of the formula 2. 4. The s, ^ λ λ ^ 5 h wash photoresist pattern and the protective layer forming composition, wherein the solvent is removed; 4] is selected from the group consisting of: Water, stinky water, sterol, ethanol, riam, and mixtures thereof. - Alcohol, Acetone, Dimethyl ° · A composition of the patented protective layer, wherein the cross-linking pattern of the cross-linking agent and the amount of the solvent are 9. Up to 99.9% by weight. ' ～1 to 10% by weight, 6. The composition for use in the protective layer of the ninth aspect of the patent application, wherein the composition is more/washing the photoresist pattern and the shape is used for In the shape of a semiconductor device: interface 'tongue agent. The following steps are included: Forming the first photoresist by forming the first layer on the semiconductor substrate on which the etched photoresist layer exposure and development layer has been formed; to form the first photoresist pattern 21 201128324, the following formula 1 to formula 3, the solution and the solution The group of the first photoresist pattern is immersed in the group of the compound containing the first photoresist pattern to clean the first photoresist pattern: [Formula 1] R1 to +MH2 1 1 η [Formula 2] [Formula 3] ΙΝΗ2 wherein, in the formulae 1 to 3, R, a chain, a branched chain or a cyclic hydrocarbon group of 1 to 15 atoms having a chain shape, a branched chain shape or a ring furnace of 0 to carbon atoms; 1 to 1G carbons having L to 1 to 1 carbonium to 5 hetero atoms may be absent or contain a hydrocarbon group 'R4 and R5 are independently a hydrogen atom or have a chain shape, a branched chain or a ring of 1 to 6 Carbon chain + chain shape, branched chain shape: there are 5 hetero atoms connected to each other to form a ring A" hydrocarbon group, L and R5 can be ^ ~ 珉%, η is 2 to 6 full helmet 屯 integer, Q An integer of from 1 to 140; Ρ, ', to 250 by applying the cleaned first photoresist pattern to a 15 〇i 2 (hardened baking) to form a protective layer 丨... forming a a second photoresist layer; and 22 201128324, to form a second photoresist pattern between the second photoresist layer by exposing and displaying the first photoresist pattern. twenty three