CN109298600A - Amplification type I-line light resistance composition - Google Patents
Amplification type I-line light resistance composition Download PDFInfo
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- CN109298600A CN109298600A CN201710614701.8A CN201710614701A CN109298600A CN 109298600 A CN109298600 A CN 109298600A CN 201710614701 A CN201710614701 A CN 201710614701A CN 109298600 A CN109298600 A CN 109298600A
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
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Abstract
A kind of amplification type I-line light resistance composition, comprising: a polyhydroxystyrene derivatives resin；One smooth acid initiator；And a small molecule promotor, it is any compound as shown in following formula (I-1) to formula (I-3):Wherein, X1To X7、R1To R12, n1, n2 and m be defined as in the description.
Description
Technical field
This disclosure relates to a kind of amplification type I-line light resistance composition, more particularly, to it is a kind of with excellent resolution and
The amplification type I-line light resistance composition of high sensitivity characteristic.
Background technique
In contemporary semiconductor yellow light technique, such as in the technique of thin film transistor base plate, used exposure machine exposure
Area is big, and opposite lens area is also larger, cause the intensity of light source it is low with lens numerical aperture (numerical aperture,
N.A. it is worth) it is low.Therefore, in order to cooperate this machine disadvantage, it is often used high photosensitive type DNQ light.
With presently, eurymeric DNQ photoresist is always in Thin Film Transistor-LCD (TFT-LCD) yellow light technique
Important critical material, but the technique of such photoresist has been limited to 2 μm of resolution, and resulting figure under 1.5 μm of film thickness
Shape can not have vertical side wall.If conversion uses amplification type photoresist, sensitivity can be not only further increased, lowers the process time,
Also the vertical product of side wall can be obtained.However, amplification type photoresist separately plus after exposing together need to bake (PEB) technique to stablize line width and subtract
Remained after few photoresist development, but because after exposing curing process it is many and diverse, it is virtually impossible to it is after the yellow light technique of existing TFT-LCD to increase more
Curing process replaces script DNQ photoresist after exposing together.
Therefore, if can develop one kind can need not can improve script DNQ light by the amplification type photoresist of curing process after exposing
The limited problem of resolution is hindered, the limitation of curing process after more avoidable existing amplification type light group needs to expose, and be more applicable for existing
Some semiconductor technologies.
Summary of the invention
The main purpose of the disclosure is to provide a kind of amplification type I-line light resistance composition, with excellent resolution
And high sensitivity characteristic.
The amplification type I-line light resistance composition of the disclosure, comprising: a polyhydroxystyrene derivatives resin；One light acid draws
Send out agent；And a small molecule promotor, it is any compound as shown in following formula (I-1) to formula (I-3):
Wherein, X1、X2、X3、X4、X5、X6And X7Respectively stand alone asAnd RaIt is substituted or is unsubstituted
C1-20Alkyl or the C for being substituted or being unsubstituted3-30Naphthenic base or RaThe C atom adjacent with O and O and methyl are formed together one
Five yuan or hexa-atomic of heterocycle；
Every R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12Respectively hydrogen stood alone as, be substituted or be unsubstituted
C1-20Alkyl, the C for being substituted or being unsubstituted3-30Naphthenic base, the C for being substituted or being unsubstituted6-14Aryl, halogen orWherein RfFor the C for being substituted or being unsubstituted1-20Alkyl or the C for being substituted or being unsubstituted3-30Naphthenic base,
Or the Rf C atom and methyl adjacent with O and O is formed together First Five-Year Plan member or hexa-atomic heterocycle；
The C that A is a singly-bound, is substituted or is unsubstituted1-20Alkylidene, the C for being substituted or being unsubstituted3-30Cycloalkylidene,
The fluorenylidene that is substituted or is unsubstituted orWherein RbAnd RcRespectively stand alone as be substituted or
The C being unsubstituted1-20Alkyl, RdAnd ReRespectively stand alone as throughAnd RgFor the C for being substituted or being unsubstituted1-20Alkane
Base or the C for being substituted or being unsubstituted3-30Naphthenic base or RgThe C atom adjacent with O and O and methyl be formed together the First Five-Year Plan member or
Hexa-atomic heterocycle, and p1 and p2 respectively stand alone as 0 to 4 integer；
N1 and n2 respectively stand alone as integer of 1 to 3；And
M is integer of 0 to 10.
Previous amplification type photoresist need to curing process remains after exposure to stablize line width and reduce after photoresist develops separately plus together.This
Disclosed amplification type I-line light resistance composition include polycarboxylated styrene (poly (hydroxystyrene)) derivatives resin,
Have the small molecule promotor and light acid initiator of protecting group；Wherein have protecting group small molecule promotor structure in comprising multiple
Alcohol radical position is grafted upper protecting group, and in unexposed area as a dissolution inhibitor, and the protecting group is acted on by light acid after exposure
Excision, and then resin dissolution is helped, increasing rate of dissolution in exposure region as a dissolution accelerator, it is micro- can to promote yellow light whereby
The sensibility and resolution of polyhydroxystyrene derivatives resin (the positive row photoresist of amplification type) in shadow technique, therefore can exempt subsequent
Curing process is after exposure to reduce process time and cost, and the contrast of related reinforcement exposure region.In addition, in semiconductor processing,
The amplification type I-line light resistance composition of the disclosure is exposed in the FPD of low numerical aperture (numerical aperture, N.A. value)
There is high sensitivity, high-res under ray machine.Furthermore the amplification type I-line light resistance composition of the disclosure more with electroconductive ITO glass
Glass substrate has the characteristics such as good adhesion, resistance to oxalic acid wet etching.Therefore, the amplification type I-line light resistance composition of the disclosure can
Apply to be produced in the semiconductor technology of more high-res.
In an embodiment of the disclosure, small molecule promotor is small molecule promotor shown in formula (I-1).
X in an embodiment of the disclosure, in formula (I-1)1With X2It may be the same or different, R1With R2It may be the same or different,
And n1 and n2 may be the same or different；Or X1With X2It is identical, R1With R2It is identical, and n1 is identical as n2.
R in an embodiment of the disclosure, in formula (I-1)1With R2Can respectively stand alone as hydrogen, methyl, ethyl, n-propyl,
Isopropyl, normal-butyl, the second butyl, isobutyl group, tert-butyl, phenyl, cyclohexyl, fluorine, chlorine,
In an embodiment of the disclosure, the A in formula (I-1) can be a singly-bound, the C replaced through phenyl1-20Alkylidene, not
The C being substituted1-20Alkylidene, the C replaced through methyl or ethyl5-6Cycloalkylidene, the C being unsubstituted5-6Cycloalkylidene or without
Substituted fluorenylidene.
In an embodiment of the disclosure, small molecule promotor is small molecule promotor shown in formula (I-2).
In an embodiment of the disclosure, in formula (I-2), X3With X4It may be the same or different, R3、R4、R5And R6Can it is identical or
Difference, and R7、R8With R9It may be the same or different；Or X3With X4It is identical, R3、R4With R5It is identical, R6With R3、R4And R5It is identical or different,
And R7、R8With R9It is identical.
R in an embodiment of the disclosure, in formula (I-2)3、R4With R5For methyl or ethyl, R6For the benzene being substituted
Base, and R7、R8With R9For hydrogen.
In an embodiment of the disclosure, small molecule promotor is small molecule promotor shown in formula (I-3).
In an embodiment of the disclosure, in formula (I-3), X5、X6With X7It may be the same or different, R10、R11With R12It can be identical
Or it is different, and m is 1 or 2；Or X5、X6With X7It is identical, R10、R11With R12It is identical, and m is 1 or 2.
R in an embodiment of the disclosure, in formula (I-3)10、R11With R12For hydrogen.
In an embodiment of the disclosure, small molecule promotor is not limited to using single small molecule promotor, can be a variety of small
Molecule promotor, which merges, to be used.For example, formula (I-1) can be merged use with the small molecule promotor of formula (I-2).
In an embodiment of the disclosure, X1、X2、X3、X4、X5、X6And X7Respectively stand alone asWherein RaIt can
For the C being unsubstituted1-3Alkyl, through C1-3The C that alkoxy replaces1-3Alkyl, the C being unsubstituted5-7Naphthenic base or RaWith O and O
Adjacent C atom and methyl are formed together First Five-Year Plan member or hexa-atomic heterocycle；Or RaIt can be the C being unsubstituted2-3Alkyl, through C1-3
The C that alkoxy replaces2-3Alkyl, the cyclohexyl being unsubstituted or RaThe C atom adjacent with O and O and methyl are formed together the First Five-Year Plan
First or hexa-atomic heterocycle being unsubstituted.In the disclosure, X1、X2、X3、X4、X5、X6And X7Specific example include, but not
It is limited to,
In an embodiment of the disclosure,In RfIt can be the C being unsubstituted1-3Alkyl, through C1-3Alcoxyl
The C that base replaces1-3Alkyl or the C being unsubstituted5-7Naphthenic base or RfThe C atom adjacent with O and O and methyl are formed together one
Five yuan or hexa-atomic of heterocycle；Or RfIt can be the C being unsubstituted2-3Alkyl, through C1-3The C that alkoxy replaces2-3Alkyl or without
Substituted cyclohexyl or RfThe C atom adjacent with O and O and methyl are formed together First Five-Year Plan member or the hexa-atomic heterocycle being unsubstituted
Base.
In an embodiment of the disclosure,In RgIt can be the C being unsubstituted1-3Alkyl, through C1-3Alcoxyl
The C that base replaces1-3Alkyl, the C being unsubstituted5-7Naphthenic base or RgThe C atom adjacent with O and O and methyl are formed together the First Five-Year Plan
First or hexa-atomic heterocycle；Or RgIt can be the C being unsubstituted2-3Alkyl, through C1-3The C that alkoxy replaces2-3Alkyl is unsubstituted
Cyclohexyl or RgThe C atom adjacent with O and O and methyl are formed together First Five-Year Plan member or the hexa-atomic heterocycle being unsubstituted.
In the disclosure, small molecule promotor can be selected from as the group as composed by following formula (1) to (26):
In formula (1) into formula (26), X1、X2、X3、X4、X5、X6And X7Respectively stand alone asAndFor
The specific example of the small molecule promotor of the disclosure includes, but are not limited to:
In an embodiment of the disclosure, the weight average molecular weight of polyhydroxystyrene derivatives resin can be between 3000
To between 25000.
In an embodiment of the disclosure, polyhydroxystyrene derivatives resin may include such as following formula (II-1) and (II-2)
Repetitive unit:
Wherein, RhFor the C for being substituted or being unsubstituted1-20Alkyl or the C for being substituted or being unsubstituted3-30Naphthenic base, or
RhThe C atom adjacent with O and O and methyl are formed together First Five-Year Plan member or hexa-atomic heterocycle.
Wherein, the repetitive unit of formula (II-1) repetitive unit and formula (II-2) are in the polyhydroxystyrene derivatives resin
Molar ratio can be between 1: 1 to 1: 4.
Wherein, RhIt can be the C being unsubstituted1-20Alkyl or RhThe C atom adjacent with O and O and methyl are formed together the First Five-Year Plan
First or hexa-atomic heterocycle.In an embodiment of the disclosure, RhIt can be the C being unsubstituted1-3Alkyl, through C1-3Alkoxy replaces
C1-3Alkyl or the C being unsubstituted5-7Naphthenic base or RhThe C atom adjacent with O and O and methyl be formed together the First Five-Year Plan member or
Hexa-atomic heterocycle；Or RhIt can be the C being unsubstituted2-3Alkyl, through C1-3The C that alkoxy replaces2-3Alkyl is unsubstituted
Cyclohexyl or RhThe C atom adjacent with O and O and methyl are formed together First Five-Year Plan member or the hexa-atomic heterocycle being unsubstituted.
In the disclosure, the specific example of formula (II-1) repetitive unit of polyhydroxystyrene derivatives resin includes, but
It is not limited to:
In the disclosure, previously described formula (II-1a) can be independent to formula (II-1e) or merges use.For example, poly- hydroxy benzenes
Ethylene derivative resin can include the repetitive unit of formula (II-1a), formula (II-1c) and formula (II-2) simultaneously.
In the disclosure, the type of light acid initiator has no specifically limited, as long as can promote polyhydroxystyrene derivatives
Resin carries out polymerization reaction.In an embodiment of the disclosure, light acid initiator can be as shown in following formula (III):
Wherein RxFor C1-20Alkyl.
In an embodiment of the disclosure, shown in light acid initiator such as following formula (III-1):
In the disclosure, the content of polyhydroxystyrene derivatives resin, small molecule promotor and light acid initiator has no
It is specifically limited, it can be changed according to process conditions.In an embodiment of the disclosure, amplification type I-line light resistance composition can
It include: more than or equal to 10 parts by weight and less than or equal to the polyhydroxystyrene derivatives resin of 30 parts by weight；Greater than 0 weight
Part and the small molecule promotor for being less than or equal to 10 parts by weight；And it is greater than or equal to 0.5 parts by weight and is less than or equal to 3 weight
The light acid initiator of part.
In the amplification type I-line light resistance composition of the disclosure, alkyl, alkylidene, naphthenic base, cycloalkylidene, aryl,
Arlydene is optionally replaced a substituent group or to replace, and wherein the substituent group can be alkyl, naphthenic base, halogen, alkane
Oxygroup, alkenyl, heterocycle, aryl, ester group, amido or carboxyl, but alkyl will not be again replaced alkyl.
In the amplification type I-line light resistance composition of the disclosure, so-called " halogen " includes fluorine, chlorine, bromine and iodine, preferably
For fluorine, chlorine or bromine.In the disclosure, so-called " (Asia) alkyl " includes (Asia) alkyl of straight chain and attachment, preferably includes straight
The C of chain and attachment1-20(Asia) alkyl, then good is the C for including straight chain and attachment1-12(Asia) alkyl, and being more preferably includes straight chain and branch
(Asia) C of chain1-6Alkyl；And its specific example includes, but are not limited to: (Asia) methyl, (Asia) ethyl, (Asia) propyl, (Asia) isopropyl
Base, (Asia) butyl, (Asia) isobutyl group, (Asia) second butyl, (Asia) tert-butyl.So-called " (Asia) aryl " includes hexa-atomic carbon list
Ring, 10 yuan of carbon are bicyclic, 14 membered tricyclic aromatic ring systems, and specific example includes, but are not limited to: (Asia) phenyl, (Asia) naphthalene,
(Asia) pyrenyl, (Asia) anthryl and (Asia) phenanthryl, and preferably (Asia) phenyl.So-called " (Asia) naphthenic base " word refer to unit price or
Bivalent saturated cyclic hydrocarbon group, it includes 3 to 30 carbon atom (such as C3-C12), specific example include, but are not limited to:
(Asia) cyclopropyl, (Asia) cyclobutyl, (Asia) cyclopenta, (Asia) cyclohexyl, 1 or 4 cyclohexylidene, (Asia) suberyl, (Asia) ring are pungent
Base.
In the amplification type I-line light resistance composition of the disclosure, in addition to polyhydroxystyrene derivatives resin, small molecule
It more may include a solvent outside promotor and light acid initiator.Wherein, the type and content of solvent has no specifically limited, as long as energy
Solute is set to have good solubility.In an embodiment of the disclosure, the specific example of solvent can be propylene glycol monomethyl ether
Acetate (Propylene Glycol Monomethyl Ether Acetate, PGMEA), but the disclosure is not limited to that.
In addition, the content of solvent is greater than or equal to 60 parts by weight and is less than or equal to 80 weight in an embodiment of the disclosure
Part.
In addition, in the amplification type I-line light resistance composition of the disclosure, in addition to polyhydroxystyrene derivatives resin, small
Outside molecule promotor and light acid initiator, more optionally include other additives, such as: acid inhibitor, attachment additive,
Interfacial agent etc..
Detailed description of the invention
Fig. 1 is the 1H NMR spectra figure of the compound (1-a) of disclosure preparation example 1；
Fig. 2 is the 1H NMR spectra figure of the compound (1-b) of disclosure preparation example 2；
Fig. 3 is the 1H NMR spectra figure of the compound (1-c) of disclosure preparation example 3；
Fig. 4 is the 1H NMR spectra figure of the compound (1-d) of disclosure preparation example 4；
Fig. 5 is the 1H NMR spectra figure of the compound (1-e) of disclosure preparation example 5；
Fig. 6 is the 1H NMR spectra figure of the compound (1-f) of disclosure preparation example 6.
Specific embodiment
Illustrate embodiment of the present disclosure below by way of particular specific embodiment, the personage for being familiar with this skill can be by this theory
The bright revealed content of book understands other advantages and effect of the disclosure easily.The disclosure also can be different specific by other
Embodiment is implemented or is applied, and the various details in this specification also can not depart from this hair for different viewpoints and application
Various modifications and change are carried out under bright spirit.
Unless otherwise indicated herein, otherwise singular used in specification and scope of the appended claims
" one " and "the" include one or more individuals.
Unless otherwise indicated herein, otherwise term "or" used in specification and scope of the appended claims is logical
It often include the meaning of "and/or".
Term as used herein " weight average molecular weight " is to utilize gel permeation chromatography (GPC) solvent: tetrahydrofuran
(THF), the weight average molecular weight (M for being converted into polystyrene measuredw) value.
Preparation example 1- prepare compound (1-a)
Bisphenol Z (Bisphenol Z) (4,4 '-cyclohexylene biphenols (4,4 '-Cyclohexylidenebisphenol),
MW=268,2.0g, 7.46mmol) it is dissolved in THF (15mL), by toluene-4-sulfonic acid (toluene-4-sulfonic under ice bath
Acid) (MW=190,0.14g, 0.75mmol, 0.1eq) is directly added into reaction solution, then protecting group ethyl second is added dropwise
After alkene ether (ethyl vinyl ether) (MW=72,2.426mL, 0.0254mol, 3.4eq) stirs 30 minutes, add
Enter triethylamine and terminates reaction.THF and triethylamine are removed using rotary evaporator, carries out col-umn chromatography purifying, first hexane: three
Ethylamine=4: 1 mixing is sufficiently stirred with silica gel after be configured to tubing string, then purified using hexane as liquid is purged with, by product after purification
It is dissolved in hexane, is recrystallized at 0 DEG C, white small molecule product can be obtained.Wherein, the 1H NMR light of white small molecule product
Spectrum is as shown in Figure 1.
Preparation example 2- prepare compound (1-b)
Bisphenol Z (MW=268,2.0g, 7.46mmol) is dissolved in THF (15mL), by toluene-4-sulfonic acid (MW=under ice bath
190,0.14g, 0.75mmol, 0.1eq) it is directly added into reaction solution, then protecting group 3 is added dropwise, 4- dihydro -2H- piperazine is muttered
After (3,4-dihydro-2H-pyran) (MW=84.12,6.8mL, 7.46mmol, 10eq) is stirred 30 minutes, it is added three
Ethylamine terminates reaction.THF and triethylamine are removed using rotary evaporator, col-umn chromatography purifying is carried out, first with hexane: three second
Base amine=4: 1 mixing is sufficiently stirred with silica gel after be configured to tubing string, then purified using hexane as liquid is purged with, product after purification is molten
It in hexane, is recrystallized at 0 DEG C, white small molecule product can be obtained.Wherein, the 1H NMR spectra of white small molecule product
As shown in Figure 2.
Preparation example 3- prepare compound (1-c)
9,9- bis- (3- methyl -4- hydroxy phenyl) fluorenes (Biscresolfluorene, BCF, MW=378.46,2.0g,
It 5.28mmol) is dissolved in THF (10.5mL), it is under ice bath that toluene-4-sulfonic acid (MW=190,0.2g, 1.05mmol, 0.2eq) is straight
It connects and is added in reaction solution, then protecting group ethyl vinyl ether (MW=72,1.259mL, 0.0132mol, 2.5eq) is added dropwise
After stirring ten minutes, triethylamine is added and terminates reaction.THF and triethylamine are removed using rotary evaporator, carries out tubing string
Chromatographic purifying, first with hexane: triethylamine=4: 1 mixing is sufficiently stirred with silica gel after be configured to tubing string, then using hexane as rushing
Extract purifying, is dissolved in hexane for product after purification, is recrystallized at 0 DEG C, white small molecule product can be obtained.Wherein, white
The 1H NMR spectra of color small molecule product is as shown in Figure 3.
Preparation example 4- prepare compound (1-d)
BCF (MW=378.46,2.0g, 5.28mmol) is dissolved in THF (10.5mL), by toluene-4-sulfonic acid (MW under ice bath
=190,0.2g, 1.05mmol, 0.2eq) it is directly added into reaction solution, then protecting group 3 is added dropwise, 4- dihydro -2H- piperazine is muttered
After (MW=84.12,4.816mL, 0.0528mol, 10eq) is stirred ten minutes, triethylamine is added and terminates reaction.Use rotation
Turn thickener removal THF and triethylamine, carries out col-umn chromatography purifying, first with hexane: triethylamine=4: 1 sufficiently stirs with silica gel
It is configured to tubing string after mixing mixing, then using hexane as liquid purifying is purged with, product after purification is dissolved in hexane, is carried out again at 0 DEG C
Crystallization, can be obtained white small molecule product.Wherein, the 1H NMR spectra of white small molecule product is as shown in Figure 4.
Preparation example 5- prepare compound (1-e)
Three (4- hydroxy phenyl) methane (Tris (4-hydroxyphenyl) methane, BIP-PHBZ, MW=292.33,
2.0g, 6.84mmol) be dissolved in THF (13.7mL), under ice bath by toluene-4-sulfonic acid (MW=190,0.388g, 2.04mmol,
0.3eq) be directly added into reaction solution, then be added dropwise protecting group ethyl vinyl ether (MW=72,2.944mL,
0.0307mol, 4.5eq) after stirring ten minutes, triethylamine is added and terminates reaction.THF and three is removed using rotary evaporator
Ethylamine, carry out col-umn chromatography purifying, first with hexane: triethylamine=4: 1 with silica gel be sufficiently stirred mixing after be configured to tubing string,
Again using hexane as liquid purifying is purged with, product after purification is dissolved in hexane, is recrystallized at 0 DEG C, can be obtained faint yellow small
Molecular product.Wherein, the 1H NMR spectra of faint yellow small molecule product is as shown in Figure 5.
Preparation example 6- prepare compound (1-f)
BIP-PHBZ (MW=292.33,2.0g, 6.84mmol) is dissolved in FHF (13.7mL), by toluene -4- sulphur under ice bath
Sour (MW=190,0.388g, 2.04mol, 0.3eq) is directly added into reaction solution, then protecting group 3,4- dihydro-is added dropwise
After 2H- piperazine is muttered (MW=84.12,6.24mL, 0.0684mol, 10eq) stirring ten minutes, triethylamine is added and terminates reaction.
THF and triethylamine are removed using rotary evaporator, col-umn chromatography purifying is carried out, first with hexane: triethylamine=4: 1 and silica gel
It is configured to tubing string after mixing is sufficiently stirred, then using hexane as liquid purifying is purged with, product after purification is dissolved in hexane, at 0 DEG C
It is recrystallized, faint yellow small molecule product can be obtained.Wherein, the 1H NMR spectra of faint yellow small molecule product is as shown in Figure 6.
In following Examples and Comparative Examples of the disclosure, used ingredient, structure, molecular weight and weight percent are such as
Shown in the following table 1.
Table 1
Embodiment 1-4 and comparative example
According to the following table 2, aforesaid ingredients are dissolved in solvent, then the amplification type I- of embodiment 1-4 and comparative example can be obtained
Line light resistance composition.
Table 2
| Classification | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Solvent | A | A | A | A | A |
| Resin | B | B | B | B | B |
| Small molecule promotor | - | C1 | C2 | C3 | C4 |
| Light acid initiator | D | D | D | D | D |
| Acid inhibitor | E2 | E2 | E2 | E2 | E2 |
| Adhere to additive | F | F | F | F | F |
| Interfacial agent | G | G | G | G | G |
The light resistance composition of previous embodiment 1-4 and comparative example are coated on the ito glass of 14cm x 14cm (ITO glass
Glass is through HMDS linging), it is then soft 90 seconds roasting at 90 DEG C, obtain the photoresist layer with a thickness of 1.5 μm.
By photoresist layer with Ultratech 1500stepper (Boardband；NA=0.31 it) is exposed, and selective
Curing process (PEB) (110 DEG C, 90 seconds) after ground is exposed；Development 30 seconds is carried out with 2.38%TMAH at 23 DEG C, and at 25 DEG C
With deionized water cleaning 30 seconds.Finally, the photoresist pattern after assessment exposure development.
If after exposure development, ito glass surface is remained without photoresist, then it is determined as OK；If there is photoresist residual, it is determined as
NG.As a result as shown in table 3 below.
Table 3
Such as table 3 the results show that the light resistance composition formula of embodiment of the present disclosure 1-4, even if without curing process after overexposure, warp
Exposure development metacoxal plate surface there will not be residue.However, the light resistance composition formula of comparative example, then bake after having to pass through exposure
Technique could alleviate the situation that substrate surface has residue.
In addition, more comparing the photoresist pattern after exposure development.The results show that the light resistance composition of embodiment of the present disclosure 1-4
Formula, it is still very vertical in the exposure machine performance side wall of low NA value.It is well known, however, that the photoresist of DNQ photoresist and comparative example combines
Composition formula, the obtained figure after the exposure machine exposure development of low NA value then compared with out of plumb and have trapezoidal generation.
In conclusion the amplification type I-line light resistance composition of the disclosure, by using a small molecule promotor that can be promoted
The sensibility and resolution of polyhydroxystyrene derivatives resin (the positive row photoresist of amplification type) in yellow light lithography process, therefore can exempt
Curing process is after subsequent exposure to reduce process time and cost, and the contrast of related reinforcement exposure region.In particular, the disclosure
Amplification type I-line light resistance composition has under the FPD exposure machine of low numerical aperture (numerical aperture, N.A. value)
There are high sensitivity, high-res, the effect of this can not reach for light resistance composition now.
The above is only a specific embodiment of the present invention, is not intended to restrict the invention, all in essence of the invention
Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should all be included in the protection scope of the present invention.
Claims (20)
1. a kind of amplification type I-line light resistance composition, comprising:
One polyhydroxystyrene derivatives resin；
One smooth acid initiator；And
One small molecule promotor is any compound as shown in following formula (I-1) to formula (I-3):
Wherein, X1、X2、X3、X4、X5、X6And X7Respectively stand alone asAnd RaFor the C for being substituted or being unsubstituted1-20
Alkyl or the C for being substituted or being unsubstituted3-30Naphthenic base or RaThe C atom adjacent with O and O and methyl are formed together First Five-Year Plan member
Or hexa-atomic heterocycle；
Every R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12The C for respectively standing alone as hydrogen, being substituted or being unsubstituted1-20
Alkyl, the C for being substituted or being unsubstituted3-30Naphthenic base, the C for being substituted or being unsubstituted6-14Aryl, halogen orWherein RfFor the C for being substituted or being unsubstituted1-20Alkyl or the C for being substituted or being unsubstituted3-30Naphthenic base,
Or RfThe C atom adjacent with O and O and methyl are formed together First Five-Year Plan member or hexa-atomic heterocycle；
The C that A is a singly-bound, is substituted or is unsubstituted1-20Alkylidene, the C for being substituted or being unsubstituted3-30Cycloalkylidene, through taking
Generation or the fluorenylidene that is unsubstituted orWherein RbAnd RcRespectively stand alone as be substituted or without
Substituted C1-20Alkyl, RdAnd ReRespectively stand alone asAnd RgFor the C for being substituted or being unsubstituted1-20Alkyl or
The C for being substituted or being unsubstituted3-30Naphthenic base or RgThe C atom adjacent with O and O and methyl are formed together First Five-Year Plan member or hexa-atomic
Heterocycle, and p1 and p2 respectively stand alone as 0 to 4 integer；
N1 and n2 respectively stand alone as integer of 1 to 3；And
M is integer of 0 to 10.
2. amplification type I-line light resistance composition as described in claim 1, wherein in formula (I-1), X1With X2It is identical, R1With R2
It is identical, and n1 is identical as n2.
3. amplification type I-line light resistance composition as claimed in claim 2, wherein R1With R2Respectively stand alone as hydrogen,
Methyl, ethyl, n-propyl, isopropyl, normal-butyl, the second butyl, isobutyl group, tert-butyl, phenyl, cyclohexyl, fluorine, chlorine,
4. amplification type I-line light resistance composition as claimed in claim 2, wherein A is a singly-bound, the C through phenyl substitution1-20It is sub-
Alkyl, the C being unsubstituted1-20Alkylidene, the C replaced through methyl or ethyl5-6Cycloalkylidene, the C being unsubstituted5-6Sub- cycloalkanes
Base or the fluorenylidene being unsubstituted.
5. amplification type I-line light resistance composition as described in claim 1, wherein in formula (I-2), X3With X4It is identical, R3、R4
With R5It is identical, R6With R3、R4And R5It is identical or different, and R7、R8With R9It is identical.
6. amplification type I-line light resistance composition as claimed in claim 5, wherein R3、R4With R5For methyl or ethyl, R6For warp
Substituted phenyl, and R7、R8With R9For hydrogen.
7. amplification type I-line light resistance composition as described in claim 1, wherein in formula (I-3), X5、X6With X7It is identical,
R10、R11With R12It is identical, and m is 1 or 2.
8. amplification type I-line light resistance composition as claimed in claim 7, wherein R10、R11With R12For hydrogen.
9. amplification type I-line light resistance composition as described in claim 1, wherein RaFor the C being unsubstituted1-3Alkyl, through C1-3
The C that alkoxy replaces1-3Alkyl or the C being unsubstituted5-7Naphthenic base or RaC atom and methyl one similar shape adjacent with O and O
At First Five-Year Plan member or hexa-atomic heterocycle.
10. amplification type I-line light resistance composition as claimed in claim 9, wherein X1、X2、X3、X4、X5、X6And X7It is respectively independent
For
11. amplification type I-line light resistance composition as described in claim 1, wherein the small molecule promotor is selected from by such as following formula
(1) to group composed by (26):
12. amplification type I-line light resistance composition as claimed in claim 11, wherein X1、X2、X3、X4、X5、X6And X7Respectively solely
It stands and is AndFor
13. amplification type I-line light resistance composition as claimed in claim 11, wherein the small molecule promotor is selected from by as follows
Group composed by formula (1-a) to (1-f):
14. amplification type I-line light resistance composition as described in claim 1, the wherein polyhydroxystyrene derivatives resin
Weight average molecular weight is between 3000 to 25000.
15. amplification type I-line light resistance composition as described in claim 1, the wherein polyhydroxystyrene derivatives resin packet
Include the repetitive unit such as following formula (II-1) and (II-2):
Wherein, RhFor the C for being substituted or being unsubstituted1-20Alkyl or the C for being substituted or being unsubstituted3-30Naphthenic base or RhWith O,
The C atom adjacent with O and methyl are formed together First Five-Year Plan member or hexa-atomic heterocycle.
16. amplification type I-line light resistance composition as claimed in claim 15, wherein formula (II-1) repetitive unit and formula (II-
2) molar ratio of the repetitive unit in the polyhydroxystyrene derivatives resin is between 1: 1 to 1: 4.
17. amplification type I-line light resistance composition as claimed in claim 15, wherein RhFor the C being unsubstituted1-3Alkyl, warp
C1-3The C that alkoxy replaces1-3Alkyl or the C being unsubstituted5-7Naphthenic base or RhTogether with the C atom adjacent with O and O and methyl
Form First Five-Year Plan member or hexa-atomic heterocycle.
18. amplification type I-line light resistance composition as claimed in claim 15, wherein formula (II-1) be following formula (II-1a),
(II-1b), (II-1c), (II-1d) or (II-1e):
19. amplification type I-line light resistance composition as described in claim 1, wherein light acid initiator such as following formula (III) institute
Show:
Wherein RxFor C1-20Alkyl.
20. amplification type I-line light resistance composition as described in claim 1, comprising:
More than or equal to 10 parts by weight and less than or equal to the polyhydroxystyrene derivatives resin of 30 parts by weight；
Greater than 0 parts by weight and less than or equal to the small molecule promotor of 10 parts by weight；And
More than or equal to 0.5 parts by weight and less than or equal to the light acid initiator of 3 parts by weight.
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| CN201710614701.8A CN109298600B (en) | 2017-07-25 | 2017-07-25 | Amplified I-line photoresist composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710614701.8A CN109298600B (en) | 2017-07-25 | 2017-07-25 | Amplified I-line photoresist composition |
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| CN109298600B CN109298600B (en) | 2022-03-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105330A (en) * | 2021-04-15 | 2021-07-13 | 北京科华微电子材料有限公司 | Phenolic compound, preparation method and application thereof, and photoresist |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000031020A (en) * | 1998-07-14 | 2000-01-28 | Hitachi Ltd | Patterning material and method of patterning the same |
| TW434459B (en) * | 1995-10-02 | 2001-05-16 | Shinetsu Chemical Co | Chemically amplified positive resist composition |
| CN1748181A (en) * | 2003-02-10 | 2006-03-15 | 飞索有限责任公司 | Radiation-sensitive resin composition, process for producing the same and process for producing semiconductor device therewith |
| TW200804983A (en) * | 2006-03-17 | 2008-01-16 | Sumitomo Chemical Co | Chemically amplifying positive photoresist composition |
| CN102227474A (en) * | 2009-01-29 | 2011-10-26 | 东丽株式会社 | Resin composition and display device formed using same |
| JP2014085514A (en) * | 2012-10-24 | 2014-05-12 | Sumitomo Chemical Co Ltd | Resist composition and method of producing resist pattern |
| CN104813231A (en) * | 2012-11-27 | 2015-07-29 | 富士胶片株式会社 | Photocurable composition, transfer material, cured product, method for producing cured product, method for producing resin pattern, cured film, liquid crystal display device, organic el display device, and touch panel display device |
-
2017
- 2017-07-25 CN CN201710614701.8A patent/CN109298600B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW434459B (en) * | 1995-10-02 | 2001-05-16 | Shinetsu Chemical Co | Chemically amplified positive resist composition |
| JP2000031020A (en) * | 1998-07-14 | 2000-01-28 | Hitachi Ltd | Patterning material and method of patterning the same |
| CN1748181A (en) * | 2003-02-10 | 2006-03-15 | 飞索有限责任公司 | Radiation-sensitive resin composition, process for producing the same and process for producing semiconductor device therewith |
| TW200804983A (en) * | 2006-03-17 | 2008-01-16 | Sumitomo Chemical Co | Chemically amplifying positive photoresist composition |
| CN102227474A (en) * | 2009-01-29 | 2011-10-26 | 东丽株式会社 | Resin composition and display device formed using same |
| JP2014085514A (en) * | 2012-10-24 | 2014-05-12 | Sumitomo Chemical Co Ltd | Resist composition and method of producing resist pattern |
| CN104813231A (en) * | 2012-11-27 | 2015-07-29 | 富士胶片株式会社 | Photocurable composition, transfer material, cured product, method for producing cured product, method for producing resin pattern, cured film, liquid crystal display device, organic el display device, and touch panel display device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105330A (en) * | 2021-04-15 | 2021-07-13 | 北京科华微电子材料有限公司 | Phenolic compound, preparation method and application thereof, and photoresist |
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| CN109298600B (en) | 2022-03-29 |
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