CN109557764A

CN109557764A - Chemically amplified positive photosensitive resin composition, resist pattern and method for forming the same, and electronic device

Info

Publication number: CN109557764A
Application number: CN201811092392.3A
Authority: CN
Inventors: 许智航; 刘骐铭; 施俊安
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2017-09-27
Filing date: 2018-09-19
Publication date: 2019-04-02
Anticipated expiration: 2038-09-19
Also published as: TWI742165B; TW201915607A; CN109557764B

Abstract

The invention provides a chemical amplification type positive photosensitive resin composition, a photoresist pattern and a forming method thereof, and an electronic device, wherein the chemical amplification type positive photosensitive resin composition comprises: a polyhydroxystyrene resin (A) having an acid-dissociable protecting group; a monounsaturated nitrile compound (B); a photoacid generator (C); and a solvent (D), wherein the use of the chemically amplified positive photosensitive resin composition can improve the problems of poor adhesion and taper angle.

Description

Chemical amplification positive photosensitive resin composition, photoresist pattern and forming method thereof And electronic device

Technical field

The present invention relates to a kind of chemical amplification positive photosensitive resin composition, photoresist pattern and forming method thereof and Electronic device, more particularly to a kind of chemical amplification positive photoresist that can improve adherence and the bad problem of taper angle Constituent, photoresist pattern as made from the chemical amplification positive photosensitive resin composition and forming method thereof and comprising The electronic device of the photoresist pattern.

Background technique

So far, in the field using glass substrate manufacture liquid crystal display element, it is suitable for g, h, i line exposing, valence Lattice are less expensive, sensitivity and analyticity are good, can form the photoresist of the excellent photoresist pattern of shape, mostly use greatly with phenolic aldehyde tree Rouge uses the eurymeric light resistance composition for containing quinonediazide group compound as photosensitive sexual element as alkali soluble resin (Patent Documents 1 to 4).

Now, the LCD as the secondary generation is formed simultaneously driver, digital resolution converter on one piece of glass substrate (DAC), the Integrated circuit portions such as image processing apparatus, Video Controller, RAM and display portion, i.e., the height of so-called " system LCD " The technological development of function LCD is very prevailing.

In this specification, for convenience, the substrate of integrated circuit and liquid-crystal display section will be formed on one substrate Referred to as system LCD.

In system LCD, substitutes uncrystalline silicon and the material that can be formed in 600 DEG C of low temperature process below gathers for low temperature Silicon, compared to uncrystalline silicon, the resistance of low-temperature poly-silicon is small, degree of excursion is high.Therefore, dealer it is expected that exploitation is suitable for manufacturing using low The light resistance composition of the system LCD of the poly- silicon of temperature.Photoresist used in system LCD has various reports (patent document 5 at present ~12).

It manufactures as formed by low-temperature poly-silicon when TFT, after forming poly- silicon fiml on the glass substrate with low temperature process, in the low temperature P (phosphorus) or B (boron) etc. are injected on poly- silicon fiml, in so-called " injection process ", need to inject the impurity of very high concentration.

This injection process is in the state of forming photoresist pattern on low-temperature poly-silicon glass substrate, in the item of condition of high vacuum degree It is carried out under part.But during this, because passing through heating functioin when implanted dopant, the shape of the photoresist pattern made on substrate is changed Cause certain compositions in photoresist pattern to gasify when becoming, and heating, causes to handle the problem of indoor vacuum degree declines.

The method for solving the problems, such as this very has to carry out the heating treatment step of referred to as " rear roasting " before injection process Effect." rear roasting " herein is due to carrying out (such as 200 DEG C or more under the conditions of being the temperature of heating temperature when close to injection High temperature), therefore photoresist need to have the high heat resistance characteristic in the heat treatment changing pattern form.

Therefore, for the manufacture realizationization for making system LCD, the light resistance composition that it must be sought to use has good heat-resisting Property.

Pattern dimension in addition, in system LCD, such as relative to display portion is 2~10 μm, and Integrated circuit portion is then It is formed with 0.5~2.0 μm of fine size.Therefore, light resistance composition used in manufacture system LCD removes requirement and can be formed simultaneously Other than the ability (linear) of the good fine pattern of shape and coarse patterns, more require than photoresist used in previous manufacture LCD Material has higher resolution ratio, wide (DOF) characteristic of the depth of focus with good fine pattern.

However, in the manufacturing field of liquid crystal display element, eurymeric light resistance composition institute shape used in existing system LCD At the adherence of photoresist pattern, taper angle it is bad, be easy to cause serious productivity to decline, therefore improve adherence and taper angle Bad problem is that industry is desired.

[patent document]

Patent document 1: Japanese Unexamined Patent Publication 2000-131835 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2001-075272 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2000-181055 bulletin

Patent document 4: Japanese Unexamined Patent Publication 2000-112120 bulletin

Patent document 5: Japanese Unexamined Patent Publication 2004-233846 bulletin

Patent document 6: Japanese Unexamined Patent Publication 2004-191394 bulletin

Patent document 7: Japanese Unexamined Patent Publication 2004-145207 bulletin

Patent document 8: Japanese Unexamined Patent Publication 2004-144905 bulletin

Patent document 9: Japanese Unexamined Patent Publication 2004-077999 bulletin

Patent document 10: Japanese Unexamined Patent Publication 2004-045707 bulletin

Patent document 11: Japanese Unexamined Patent Publication 2004-045618 bulletin

Patent document 12: Japanese Unexamined Patent Publication 2003-233174 bulletin

Summary of the invention

In view of this, the present invention provides a kind of chemical amplification positive photosensitive resin composition, increased using the chemistry Width type positive-type photosensitive resin composition can improve adherence and the bad problem of taper angle.

The present invention provides a kind of chemical amplification positive photosensitive resin composition, comprising: contains acid dissociation protecting group Polyhydroxystyrene resin (A), single unsaturated nitrile compound (B), photoacid generator (C) and solvent (D).

In one embodiment of this invention, the carbon atomicity of single unsaturated nitrile compound (B) is 6~30.

In one embodiment of this invention, single unsaturated nitrile compound (B) is selected from decene nitrile (Decenenitrile), the last of the ten Heavenly stems Alkene dintrile, endecatylene nitrile (Undecenitrile), dodecylene nitrile (Dodecenitrile), tridecylene nitrile (Tridecenonitrile), tetradecene nitrile (Tetradecenenitrile), hexadecene nitrile (Hexadecenenitrile), hexadecene dintrile, octadecene nitrile (Octadecenenitrile), octadecene dintrile with And two dodecylene nitrile (Eruconitrile) compound composed by group.

In one embodiment of this invention, chemical amplification positive photosensitive resin composition further includes alkali compounds (E)。

In one embodiment of this invention, alkali compounds (E) includes by formula (E-1) compound represented:

N(A)_z(B)_3-zFormula (E-1)

In formula (E-1), A respectively independently indicates the naphthenic base that alkyl, carbon number that carbon number is 4 to 20 are 3 to 20, carbon number 6 To 20 phenyl or aralkyl.B respectively independently indicates the alkyl that hydrogen atom or carbon number are 1 to 3.Z indicates integer of 1 to 3.

In one embodiment of this invention, chemical amplification positive photosensitive resin composition further includes having nitrogen-atoms Heterocyclic compound (F) is selected from the group as composed by following formula (F-1) to formula (F-4) compound represented:

In formula (F-1) into formula (F-4), G₁And G₂Separately represent hydrogen atom, acyl group or alkyl；H₁To H₉Respectively Independently represent hydrogen atom, hydroxyl, carboxylic acid group, sulfonic group, alkyl, amido, halogen atom or sulfydryl.V, w, q and s be independently Ground represents 0 to 3 integer；P and r separately represents 0 to 2 integer；And t and u separately represent 0 to 4 integer.

In one embodiment of this invention, based on the total of the polyhydroxystyrene resin (A) containing acid dissociation protecting group Usage amount is 100 parts by weight, and the content of single unsaturated nitrile compound (B) is 0.03 parts by weight to 1.0 parts by weight, photoacid generator (C) content is 0.3 parts by weight to 3 parts by weight, and the content of solvent (D) is 200 parts by weight to 1200 parts by weight.

In one embodiment of this invention, based on the total of the polyhydroxystyrene resin (A) containing acid dissociation protecting group Usage amount is 100 parts by weight, and the content of alkali compounds (E) is 0.03 parts by weight to 1.0 parts by weight.

In one embodiment of this invention, based on the total of the polyhydroxystyrene resin (A) containing acid dissociation protecting group Usage amount is 100 parts by weight, and the content of the heterocyclic compound (F) with nitrogen-atoms is 0.01 parts by weight to 0.5 parts by weight.

The present invention also provides a kind of forming method of photoresist pattern, comprising: above-mentioned chemical amplification type is coated on substrate The process of positive-type photosensitive resin composition.

The present invention more provides a kind of photoresist pattern, is formed by the forming method of above-mentioned photoresist pattern.

The present invention provides a kind of electronic device again, includes above-mentioned photoresist pattern.

It is protected because containing containing acid dissociation based on above-mentioned, of the invention chemical amplification positive photosensitive resin composition The polyhydroxystyrene resin (A) of base and single unsaturated nitrile compound (B), therefore adherence can be improved and taper angle is bad The problem of.

To make the foregoing features and advantages of the present invention clearer and more comprehensible, special embodiment below, detailed description are as follows.

Detailed description of the invention

Fig. 1 is the schematic diagram for measuring the taper angle of photoresist pattern.

[symbol description]

1: taper angle (θ)

2: photoresist pattern

3: substrate

Specific embodiment

The present invention provides a kind of chemical amplification positive photosensitive resin composition, comprising: contains acid dissociation protecting group Polyhydroxystyrene resin (A), single unsaturated nitrile compound (B), photoacid generator (C) and solvent (D).In addition, this hair Bright chemical amplification positive photosensitive resin composition more may include alkali compounds (E), or the heterocycle with nitrogen-atoms Compound (F).

It will be detailed below each ingredient for chemical amplification positive photosensitive resin composition of the invention.

It is described herein to be, it is that acrylic acid and/or methacrylic acid are indicated with (methyl) acrylic acid below, and with (methyl) Acrylate indicates acrylate and/or methacrylate；Similarly, with (methyl) acryloyl group indicate acryloyl group and/ Or methylacryloyl.

Polyhydroxystyrene resin (A) containing acid dissociation protecting group

In polyhydroxystyrene resin (A) containing acid dissociation protecting group, so-called polyhydroxystyrene resin (protection Before) it is comprising the polymer as formed by hydroxy styrenes (object is polymerized alone in hydroxy styrenes) and its derivative.Poly- hydroxyl so Base styrene is for example: vinylphenol is polymerized alone object, vinylphenol, can be with the copolymerization of the comonomer of its combined polymerization Object etc..In this, comonomer for example: (methyl) acrylic acid derivative, (methyl) acrylonitrile, styrene, α-methylstyrene, Styrene derivatives such as p-methylstyrene, ortho-methyl styrene, p-methoxystyrene, p- chlorostyrene etc..Poly- hydroxyl Object is polymerized alone with hydroxy styrenes among base styrene, hydroxy styrenes-styrol copolymer is preferred.

In polyhydroxystyrene resin (A) containing acid dissociation protecting group, at least part of hydrogen of full phenolic hydroxyl group Atom shows alkali slightly solubility or alkali-insoluble with the substitution of acid dissociation protecting group, by the acid dissociation protecting group from phenol Hydroxyl dissociation, the person that becomes alkali-soluble.

Polyhydroxystyrene resin (A) containing acid dissociation protecting group can be by making do not have the poly- of acid dissociation protecting group Hydroxy styrenes resin (polyhydroxystyrene resin before protection) carries out instead with the compound for being equivalent to acid dissociation protecting group It answers and obtains.

In addition, so-called hydroxy styrenes also includes its derivative.Specific hydroxystyrene recurring units are by following formula (A- 1) shown in:

Formula (A-1), R⁰For hydrogen atom or low alkyl group；K indicates integer of 1 to 3.

R⁰For hydrogen atom or low alkyl group (such as carbon number be 1 to 5 linear or branched alkyl group, preferably methyl), preferably For hydrogen atom.The position of hydroxyl, can for ortho position, meta position, contraposition it is any, from can obtain easily, and it is cheap for, with Contraposition is preferred.

Also, styrene includes phenyl ring not by alkyl-substituted styrene and benzene in hydroxy styrenes-styrol copolymer The compound that ring is replaced by the low alkyl group that carbon number is 1 to 5.The number of the low alkyl group of substituent group is 1 to 3.

Acid dissociation protecting group in polyhydroxystyrene resin (A) containing acid dissociation protecting group, as long as can be with The acid dissociation person caused by aftermentioned photoacid generator (C), such as: 1- ethoxyl methyl, 1- ethoxyethyl group, 1- third The alkoxies alkane such as oxygroup methyl, 1- Among, 1- n-butoxy methyl, 1- isobutoxymethyl, 1- t-butoxymethyl Base；The alkoxy carbonyl alkyls such as the carbon-based methyl of tert-butoxycarbonyl, tert-butoxy, tert-butoxycarbonylethyl；Tetrahydrofuran base； THP trtrahydropyranyl；The acetal radical of straight-chain or branched；Cyclic acetal base；Trimethyl silyl, triethylsilyl, three Trialkylsilkls such as phenyl silyl groups etc..

The preferred range of the weight average molecular weight (Mw) of polyhydroxystyrene resin before above-mentioned protection be 1,000~ It 200,000, is more preferably 2,000~50,000, most preferably 3,000~30,000.

When in chemical amplification positive photosensitive resin composition do not include the poly- hydroxy benzenes containing acid dissociation protecting group When vinyl (A), the taper angle that chemical amplification positive photosensitive resin composition is formed by photoresist pattern is bad.

Single unsaturated nitrile compound (B)

List unsaturated nitrile compound (B) used in this case, as long as chemical amplification positive photoresist can be made to form Object is formed by the adherence of photoresist pattern, taper angle improves, and type is not intended to limit, such as: acrylonitrile (Acrylonitrile), butene nitrile (Butenitrile), maleonitrile, allyl acetonitrile (Pentenenitrile), glutaconic nitrile, Hexene nitrile (Hexenenitrile), hexene dintrile, heptene nitrile (Heptenenitrile), heptene dintrile, octenes nitrile (Octenonitrile), octene dintrile, nonenyl nitrile (Nonenenitrile), nonene dintrile, decene nitrile (Decenenitrile), decene dintrile, endecatylene nitrile (Undecenitrile), dodecylene nitrile (Dodecenitrile), Tridecylene nitrile (Tridecenonitrile), tetradecene nitrile (Tetradecenenitrile), hexadecene nitrile (Hexadecenenitrile), hexadecene dintrile, octadecene nitrile (Octa decenenitrile), octadecene dintrile And two dodecylene nitrile (Eruconitrile).

Single unsaturated nitrile compound (B) can further enumerate are as follows: 2- butene nitrile, 3- butene nitrile, 2- maleonitrile, 2- amylene Nitrile, 3 pentene nitrile, allyl acetonitrile, 5- hexene nitrile ,-hexene dintrile, 6- heptene nitrile, 3- heptene dintrile, 6- octenes nitrile, 3- octene two Nitrile, 4- octene dintrile, 2- nonenyl nitrile, 6- nonenyl nitrile, 9- decene nitrile, 10- endecatylene nitrile, 11- dodecylene nitrile, 12- 12 Carbene nitrile, 2- tridecylene nitrile, 12- tridecylene nitrile, 7- tetradecene nitrile, 13- tetradecene nitrile, 3- hexadecene nitrile, 4- Hexadecene nitrile, 15- hexadecene nitrile, 6- hexadecene dintrile, 9- octadecene nitrile, 9- octadecene dintrile, 13- 22 Carbene nitrile.

The carbon atom number of above-mentioned list unsaturated nitrile compound (B) is preferably 6 to 30, more preferably 10 to 22.

Preferred embodiment such as 9- decene nitrile, 10- endecatylene nitrile, 12 carbon of 11- of above-mentioned list unsaturated nitrile compound (B) Alkene nitrile, 12- dodecylene nitrile, 2- tridecylene nitrile, 12- tridecylene nitrile, 7- tetradecene nitrile, 13- tetradecene nitrile, 3- ten Six carbene nitriles, 4- hexadecene nitrile, 15- hexadecene nitrile, 6- hexadecene dintrile, 9- octadecene nitrile, 9- octadecene two Nitrile, bis- dodecylene nitrile of 13-.

When not including list unsaturated nitrile compound (B) in chemical amplification positive photosensitive resin composition, chemistry increases It is bad that width type positive-type photosensitive resin composition is formed by the adherence of photoresist pattern, taper angle.

When in chemical amplification positive photosensitive resin composition comprising single unsaturated nitrile compound (B), and the list insatiable hunger When carbon atomicity with nitrile compound (B) is 6 to 30, chemical amplification positive photosensitive resin composition is formed by photoresist The adherence of pattern, taper angle are preferable.

Total usage amount based on the polyhydroxystyrene resin (A) containing acid dissociation protecting group is 100 parts by weight, The content of the list unsaturated nitrile compound (B) is 0.03 parts by weight to 1.0 parts by weight, preferably 0.04 parts by weight to 0.9 weight Measure part, more preferably 0.05 parts by weight to 0.8 parts by weight.

Photoacid generator (C)

Photoacid generator (C) is the compound that acid is generated by the irradiation of actinic ray or radioactive ray, as long as that can lead to The compound that light directly or indirectly generates acid is crossed, is not particularly limited.As photoacid generator (C), preferably following institute First illustrated~the 5th form acid producing agent.Hereinafter, to the photoacid generator used is suitble in photosensitive resin composition (C) preferably in is illustrated in the form of first to the 5th.

As the first form of photoacid generator (C), following formula (C-1) compound represented can be enumerated:

In formula (C-1), X¹Indicate that the sulphur atom or iodine atom of g valence, g are 1 or 2.H indicates the repetition list of the structure in parantheses First number.W¹For with X¹The organic group of bond indicates heterocycle, carbon that aryl, carbon atom number that carbon atom number is 6 to 30 are 4 to 30 The alkynyl that the alkenyl or carbon atom number that alkyl that atomicity is 1 to 30, carbon atom number are 2 to 30 are 2 to 30, W¹It can be via alkane Base, hydroxyl, alkoxy, alkyl carbonyl, aromatic carbonyl, alkoxy carbonyl group, aryloxy carbonyl, fragrant thiocarbonyl group, acyloxy, arylthio, alkylthio group, Aryl, heterocycle, aryloxy group, alkyl sulfinyl, fragrant sulfinyl, alkane sulfonyl, arylsulfonyl, alkylene oxide group, amido, cyano, At least one kind of substitution selected in group formed by nitro and halogen.W¹Number be g+h (g-1)+1, W¹Can distinguish it is mutually the same or It is different.Also, 2 or more W¹It can be bonded directly with one another or via-O- ,-S- ,-SO- ,-SO₂-、-NH-、-NW²-、-CO-、- It includes X that COO- ,-CONH-, the alkylidene that carbon atom number is 1 to 3 or phenylene, which are bonded and are formed,¹Ring structure.W²For carbon original The aryl that the alkyl or carbon atom number that subnumber is 1 to 5 are 6 to 10.

X²For structure shown in following formula (C-1a):

In formula (C-1a), X⁴Indicate the arlydene or carbon that alkylidene, carbon atom number that carbon atom number is 1 to 8 are 6 to 20 The miscellaneous base of divalent that atomicity is 8 to 20, X⁴Alkoxy that the alkyl that can be 1 to 8 via carbon atom number, carbon atom number are 1 to 8, carbon At least one kind of substitution selected in group formed by aryl, hydroxyl, cyano, nitro and the halogen that atomicity is 6 to 10.X⁵Indicate- O-、-S-、-SO-、-SO₂-、-NH-、-NW²,-CO- ,-COO- ,-CONH-, the alkylidene or sub- benzene that carbon atom number is 1 to 3 Base.H indicates the number of repeat unit of the structure in parantheses.H+1 X⁴And h X⁵It can distinguish identical or different.W²It is and above-mentioned definition It is identical.

(X³)^-For to ion (counter ion), can enumerate fluoroalkyl fluorophosphoric acid shown in following formula (C-1b) yin Borate anion shown in ion or following formula (C-1c):

[(W³)_jPF_6-j]^-Formula (C-1b)

In formula (C-1b), W³The alkyl that the hydrogen atom of 80% or more expression replaces through fluorine atom.J indicates its number, be 1 to 5 integer.J W³It can distinguish identical or different.

In formula (C-1c), W⁴~W⁷Independently indicate fluorine atom or phenyl, a part of the hydrogen atom in the phenyl or complete It portion can be via at least one kind of substitution selected in group formed by fluorine atom and trifluoromethyl.

As the ion in formula (C-1) compound represented, triphenyl sulphur, three-p-methylphenyl sulphur, 4- (benzene can be enumerated Sulfenyl) phenyl diphenyl sulphur, bis- [4- (diphenylsulfidyl) phenyl] thioethers, bis- [4- { bis- [4- (2- hydroxy ethoxy) phenyl] sulphur Base } phenyl] thioether, bis- { 4- [bis- (4- fluorophenyl) sulfenyls] phenyl } thioethers, 4- (4- benzoyl -2- chlorophenylsulfanyl) phenyl pair (4- fluorophenyl) sulphur, 7- isopropyl -9- Oxy-1 0- thia -9,10- dihydroanthracene -2- two-p-methylphenyl of base sulphur, 7- isopropyl - 9- Oxy-1 0- thia -9,10- dihydroanthracene -2- base diphenyl sulphur, 2- [(diphenyl) sulfenyl] thioxanthone, 4- [4- (4- three-level Butylbenzoyl) thiophenyl] two-p-methylphenyl of phenyl sulphur, 4- (4- benzoylphenylsulfanyl) phenyl diphenyl sulphur, diphenyl Phenylacetyl group sulphur, 4- hydroxyphenylmethyl benzyl sulphur, 2- naphthyl methyl (1- carbethoxyl group) ethyl sulphur, 4- hydroxyphenylmethyl benzene second Acyl group sulphur, phenyl [4- (4- biphenyl sulfenyl) phenyl] 4- biphenyl sulphur, phenyl [4- (4- biphenyl sulfenyl) phenyl] 3- biphenyl sulphur, [4- (4- acetyl thiophenyl) phenyl] diphenyl sulphur, octadecyl methyl phenylacetyl group sulphur, diphenyl iodine, two-p-methylphenyl iodine, bis- (4- Dodecyl phenyl) iodine, bis- (4- methoxyphenyl) iodine, (4- octyloxyphenyl) phenyl-iodide, bis- (12 oxygroup of 4-) phenyl-iodides, 4- (14 oxygroup of 2- hydroxyl) phenyl iodine, 4- cumenyl (p-methylphenyl) iodine or 4- isobutylphenyl (p-methylphenyl) iodine etc..

In ion in above-mentioned formula (C-1) compound represented, following formula (C- can be enumerated as preferable ion Sulphion shown in 1d):

In formula (C-1d), W⁸It independently indicates by hydrogen atom, alkyl, hydroxyl, alkoxy, alkyl carbonyl, alkane carbonyloxy group, alkane Oxygen carbonyl, halogen atom, the aryl that can have substituent group, the base selected in group formed by aromatic carbonyl.X²It indicates and above-mentioned formula (C-1) In X²Identical meaning.

As the specific example of sulphion shown in above-mentioned formula (C-1d), can enumerate 4- (thiophenyl) phenyl diphenyl sulphur, Bis- (4- fluorophenyl) sulphur of 4- (4- benzoyl -2- chlorophenylsulfanyl) phenyl, 4- (4- benzoylphenylsulfanyl) phenyl diphenyl sulphur, Phenyl [4- (4- biphenyl sulfenyl) phenyl] 4- biphenyl sulphur, phenyl [4- (4- biphenyl sulfenyl) phenyl] 3- biphenyl sulphur, [4- (4- acetyl Thiophenyl) phenyl] diphenyl sulphur, diphenyl [4- (to three thiophenyls) phenyl] diphenyl sulphur.

In fluoroalkyl fluorophosphoric acid anion shown in above-mentioned formula (C-1b), W³Indicate the alkyl replaced through fluorine atom, preferably Carbon atom number be 1~8, more preferably carbon atom number be 1~4.As the specific example of alkyl, methyl, ethyl, third can be enumerated The straight chained alkyls such as base, butyl, amyl, octyl；The branched alkyl groups such as isopropyl, isobutyl group, secondary butyl, three-level butyl；Even ring Naphthenic base such as propyl, cyclobutyl, cyclopenta, cyclohexyl etc., the hydrogen atom of alkyl is substituted is usually for the ratio of fluorine atom 80% or more, preferably 90% or more, more preferably 100%.If the Replacement rate of fluorine atom is not up to 80%, above-mentioned formula (C-1) institute The acid strength of the fluoroalkyl fluorophosphate shown can reduce.

Particularly good W³Be 1~4 for carbon atom number, and the Replacement rate of fluorine atom be 100% straight-chain or branch-like it is complete Fluoroalkyl can enumerate CF as specific example₃、CF₃CF₂、(CF₃)₂CF、CF₃CF₂CF₂、CF₃CF₂CF₂CF₂、(CF₃)₂CFCF₂、 CF₃CF₂(CF₃)CF、(CF₃)₃C。W³Number j be 1~5 integer, preferably 2~4, particularly good is 2 or 3.

As the specific example of preferable fluoroalkyl fluorophosphoric acid anion, [(CF can be enumerated₃CF₂)₂PF₄]^-、[(CF₃CF₂)₃PF₃]^-、[((CF₃)₂CF)₂PF₄]^-、[((CF₃)₂CF)₃PF₃]^-、[(CF₃CF₂CF₂)₂PF₄]^-、[(CF₃CF₂CF₂)₃PF₃]^-、 [((CF₃)₂CFCF₂)₂PF₄]^-、[((CF₃)₂CFCF₂)₃PF₃]^-、[(CF₃CF₂CF₂CF₂)₂PF₄]^-Or [(CF₃CF₂CF₂)₃PF₃]^-, In these, particularly good is [(CF₃CF₂)₃PF₃]^-、[(CF₃CF₂CF₂)₃PF₃]^-、[((CF₃)₂CF)₃PF₃]^-、[((CF₃)₂CF)₂PF₄]^-、[((CF₃)₂CFCF₂)₃PF₃]^-Or [((CF₃)₂CFCF₂)₂PF₄]^-。

As the preferred embodiments of borate anion shown in above-mentioned formula (C-1c), four (pentafluorophenyl group) boron can be enumerated Acid group ([B (C₆F₅)₄]^-), four [(trifluoromethyl) phenyl] borate ([B (C₆H₄CF₃)₄]^-), bis- (pentafluorophenyl group) boric acid of difluoro Root ([(C₆F₅)₂BF₂]^-), trifluoro (pentafluorophenyl group) borate ([(C₆F₅)BF₃]^-), four (difluorophenyl) borate ([B (C₆H₃F₂)₄]^-) etc..In these, particularly good is four (pentafluorophenyl group) borate ([B (C₆F₅)₄]^-)。

As the second form of photoacid generator (C), bis- (the trichloromethyl) -6- piperonyls -1,3 of 2,4-, 5- tri- can be enumerated Bis- (the trichloromethyl) -6- of piperazine, 2,4- [2- (2- furyl) vinyl] symmetrical triazine, bis- (trichloromethyl) -6- [2- (5- of 2,4- Methyl -2- furyl) vinyl] symmetrical triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (5- ethyl -2- furyl) vinyl] Symmetrical triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (5- propyl -2- furyl) vinyl] symmetrical triazine, bis- (three chloromethanes of 2,4- Base) -6- [2- (3,5- Dimethoxyphenyl) vinyl] symmetrical triazine, bis- (trichloromethyl) -6- [2- (the 3,5- diethoxies of 2,4- Base phenyl) vinyl] symmetrical triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (3,5- dipropoxy phenyl) vinyl] symmetrical three Bis- (the trichloromethyl) -6- of piperazine, 2,4- [2- (3- methoxyl group -5- ethoxyl phenenyl) vinyl] symmetrical triazine, bis- (three chloromethanes of 2,4- Base) the symmetrical triazine of -6- [2- (3- methoxyl group -5- propoxyphenyl) vinyl], the [(Asia 3,4- 2- bis- (the trichloromethyl) -6- of 2,4- Methylenedioxy group phenyl) vinyl] symmetrical triazine, bis- (the trichloromethyl) -6- (3,4- methylenedioxyphenyl) of 2,4- symmetrically triazine, 2,4- is bis--and trichloromethyl -6- (the bromo- 4- methoxyl group of 3-) symmetrical triazine of phenyl, 2,4- be bis--trichloromethyl -6- (the bromo- 4- methoxy of 2- Base) the symmetrical triazine of phenyl, 2,4- be bis--and trichloromethyl -6- (the bromo- 4- methoxyl group of 2-) symmetrical triazine of styryl phenyl, 2,4- be bis- - Trichloromethyl -6- (the bromo- 4- methoxyl group of 3-) symmetrical triazine of styryl phenyl, bis- (three chloromethanes of 2- (4- methoxyphenyl) -4,6- Base) -1,3,5- triazine, bis- (the trichloromethyl) -1,3,5- triazines of 2- (4- methoxyl group naphthalene) -4,6-, 2- [2- (2- furyl) second Alkenyl] bis- (the trichloromethyl) -1,3,5- triazines of -4,6-, 2- [2- (5- methyl -2- furyl) vinyl] bis- (three chloromethanes of -4,6- Base) -1,3,5- triazine, 2- [2- (3,5- Dimethoxyphenyl) vinyl] bis- (trichloromethyl) -1,3,5- triazines of -4,6-, 2- [2- (3,4- Dimethoxyphenyl) vinyl] bis- (trichloromethyl) -1,3,5- triazines of -4,6-, 2- (3,4- methylenedioxybenzenes Base) bis- (the trichloromethyl) -1,3,5- triazines of -4,6-, three (1,3- dibromopropyl) -1,3,5- triazines, three (2,3- dibromopropyls) - The following formula (C-2) such as the halogen-containing triaizine compounds such as 1,3,5- triazine and three (2,3- dibromopropyl) isocyanuric acid esters Shown in halogen-containing triaizine compounds.

In formula (C-2), W⁹~W¹¹Independently it is expressed as alkylhalide group.

Also, the tertiary form as photoacid generator (C), can enumerate α-(tolysulfonyl oxygroup imido grpup)-phenylacetonitrile, α-(phenylsulfonyloxy imido grpup) -2,4 dichloro benzene base acetonitrile, α-(phenylsulfonyloxy imido grpup) -2,6- dichlorophenyl acetonitrile, α-(2- chloro benzenesulfonyloxy imido grpup) -4- methoxyphenylacetonitrile, α-(ethylsulfonyloxy imido grpup) -1- chlorine pentenyl second Nitrile and following formula (C-3) compound represented containing sulfonic acid oximido.

In formula (C-3), W¹²Indicate 1 valence, divalent or trivalent organic group, W¹³Expression is substituted or unsubstituted saturated hydrocarbons Base, unsaturated alkyl or aromatic series compound base, n indicate the number of repeat unit of the structure in parantheses.

In above-mentioned formula (C-3), aromatic series compound basis representation makes aromatic compound show distinctive physics, chemically The base of the compound of matter can enumerate the heteroaryls such as the aryl such as phenyl, naphthalene or furyl, thienyl.These can also be in ring Above with 1 or more substituent group appropriate, such as halogen atom, alkyl, alkoxy, nitro etc..Also, W¹³Particularly good is carbon atom The alkyl that number is 1 to 6, can enumerate methyl, ethyl, propyl, butyl.Especially with W¹²For aromatic series compound base, W¹³For carbon atom The compound for the alkyl that number is 1 to 4 is preferable.

As acid producing agent shown in above-mentioned formula (C-3), as n=1, W can be enumerated¹²For phenyl, aminomethyl phenyl, methoxyl group Phenyl is any, W¹³For the compound of methyl, α-(mesyloxy imido grpup) -1- phenylacetonitrile, α-can be specifically enumerated (mesyloxy imido grpup) -1- (p-methylphenyl) acetonitrile, α-(mesyloxy imido grpup) -1- (p- methoxyphenyl) second Nitrile, [2- (the third sulfonyloxy imido grpup) -2,3- dihydroxy thiophene -3- subunit] (o-tolyl) acetonitrile etc..As n=2, as Acid producing agent shown in above-mentioned formula (C-3) can specifically enumerate the generation of acid shown in following formula (C-3-1)~formula (C-3-8) Agent:

In addition, the 4th form as photoacid generator (C), can enumerate the salt that cationic portion has naphthalene nucleus.It should " tool Have naphthalene nucleus " refer to structure derived from naphthalene, it is intended that the structure of at least two ring, and the meaning of the armaticity of they can be maintained.It should Naphthalene nucleus can also have the straight chain that the alkyl, hydroxy, carbon atom number of the straight-chain or branch-like that carbon atom number is 1 to 6 are 1 to 6 The substituent group of shape or the alkoxy of branch-like etc..Structure derived from naphthalene nucleus can be 1 valence base (free valence is 1), can also be 2 More than valence base (free valence is 2), more satisfactory is 1 valence base (only, at this point, being to deduct the part closed with above-mentioned substituent group bond To calculate free valence).Naphthalene nucleus number is preferably 1~3.

There is the cationic portion of the salt of naphthalene nucleus as such cationic portion, preferably shown in following formula (C-4) Structure:

In formula (C-4), W¹⁴~W¹⁶In at least 1 indicate following formula (C-4a) shown in base, remaining indicate carbon atom number be The straight-chain that 1 to 6 straight-chain or the alkyl of branch-like, the phenyl that can have substituent group, hydroxy or carbon atom number are 1 to 6 Or the alkoxy of branch-like.Alternatively, W¹⁴~W¹⁶One of for base shown in following formula (C-4a), both remaining is only respectively It stands as carbon atom number W¹⁴~W¹⁶The alkylidene of straight-chain or branch-like, these end can be bonded and annular in shape.

In formula (C-4a), W¹⁷、W¹⁸Independently indicate hydroxy, the straight-chain or branch-like that carbon atom number is 1 to 6 Alkoxy or carbon atom number be 1 to 6 straight-chain or branch-like alkyl, W¹⁸It indicates singly-bound or can have the carbon of substituent group The alkylidene of straight-chain or branch-like that atomicity is 1 to 6.L and m independently indicates that 0~2 integer, l+m are 3 or less. Work as W¹⁷There are it is a plurality of when, they can be mutually the same or different.Work as W¹⁸There are it is a plurality of when, they can be mutually the same or different.

Above-mentioned W¹⁴~W¹⁶The number of base shown in above-mentioned formula (C-4a), the stability viewpoint based on compound are preferable in the middle It is 1, remaining is the alkylidene of the straight-chain that carbon atom number is 1 to 6 or branch-like, these end can be bonded and annular in shape. At this point, above-mentioned 2 alkylidenes may include sulphur atom and constitute 3~9 Yuans rings.The number for constituting the atom (sulfur atom-containing) of ring is preferable It is 5~6.

Also, oxygen atom can be enumerated (at this point, former with the carbon of composition alkylidene as the substituent group that above-mentioned alkylidene can have Carbonyl is collectively formed in son), hydroxy etc..

Also, hydroxy, the straight-chain of carbon atom number 1~6 or branch-like can be enumerated as the substituent group that phenyl can have Alkoxy, the straight-chain of carbon atom number 1~6 or alkyl of branch-like etc..

Category is suitable as these cationic portions person, following formula (C-4b), (C-4c) those shown can be enumerated, especially with following formula (C-4c) structure shown in is preferred.

It can be salt compounded of iodine or sulfosalt as such cationic portion；More satisfactory based on viewpoints such as sour generation efficiencies is sulfosalt.

To more satisfactory for can shape for being suitable as the anion part person of salt of the cationic portion with naphthalene nucleus At the anion of sulfosalt.

It is part or all of perfluorinated fluoroalkyl sulfonic acids of hydrogen atom as the anion part of such acid producing agent Ion or aryl sulfonic acid ion.

Alkyl in fluoroalkyl sulfonic acids ion can be straight-chain, branch-like or the ring-type that carbon atom number is 1 to 20, based on production The volume size and its diffusion length of raw acid, preferably carbon atom number are 1 to 10.Especially in branch-like or ring-type person because of diffusion Apart from short and preferable.Also, methyl, ethyl, propyl, butyl, octyl etc. can be enumerated as preferable for by can inexpensively synthesize Person.

Aryl in aryl sulfonic acid ion is the aryl that carbon atom number is 6 to 20, and can enumerate can take through alkyl, halogen atom Phenyl, the naphthalene in generation.In particular, for by can inexpensively synthesize, preferably carbon atom number be 6 to 10 aryl.As preferable The specific example of person can enumerate phenyl, tosyl, ethylphenyl, naphthalene, methyl naphthalene etc..

Fluorination in above-mentioned fluoroalkyl sulfonic acids ion or aryl sulfonic acid ion, when part or all of hydrogen atom is perfluorinated Rate is preferably 10~100%, more preferably 50~100%, especially the winner with fluorine atom substitution whole hydrogen atoms, because of the intensity of acid Enhancing and it is preferable.Belong to such person, can specifically enumerate triflate, perfluor butanesulfonate, perfluorooctane sulfonate ester, perfluor Benzene sulfonate etc..

In these, as preferable anion part, following formula (C-4d) those shown can be enumerated:

W²⁰SO₃ ^-Formula (C-4d)

In formula (C-4d), W²⁰For base shown in following formula (C-4e), (C-4f) and (C-4g).

-C_xF_2x+1Formula (C-4e)

In formula (C-4e), x indicates 1~4 integer.In formula (C-4f), W²¹Indicate hydrogen atom, hydroxy, carbon atom be 1 to The alkoxy of straight-chain or branch-like that 6 straight-chain or the alkyl of branch-like or carbon atom number are 1 to 6, y expression 1~ 3 integer.In these, triflate, perfluor butanesulfonate are preferably based on safety point.

Also, as anion part, it is possible to use nitrogenous person shown in following formula (C-4h), formula (C-4i).

In formula (C-4h), formula (C-4i), X^aIndicate the straight-chain that replaces through fluorine atom of at least one hydrogen atom or branch-like Alkylidene, the carbon atom number of the alkylidene are 2~6, preferably 3~5, and most preferably carbon atom number is 3.Also, Y^a、Z^aIndependently Indicating the alkyl for the straight-chain or branch-like that at least one hydrogen atom replaces through fluorine atom, the carbon atom number of the alkyl is 1~10, Preferably 1~7, more preferably 1~3.

X^aAlkylidene carbon atom number or Y^a、Z^aAlkyl carbon atom number it is smaller, the dissolubility of organic solvent is got over Well, therefore preferably.

Also, X^aAlkylidene or Y^a、Z^aAlkyl in, through fluorine atom replace hydrogen atom number it is more, sour intensity is got over By force, therefore preferably.The ratio namely fluorination rate of fluorine atom in the alkylidene or alkyl are preferably 70~100%, more preferably 90 ~100%, the perfluorinated alkylidene or perfluoroalkyl that most preferably all hydrogen atoms replace through fluorine atom.

Belong to and be suitable as the salt person that such cationic portion has naphthalene nucleus, following formula (C-4j), formula (C-4k) can be enumerated Compound represented:

Furthermore as the 5th form of photoacid generator (C), can enumerate bis- (p-toluenesulfonyl) diazomethanes, it is bis- (1, 1- dimethylethylsulfonyl) diazomethane, bis- (cyclohexylsulfonyl) diazomethanes, bis- (2,4- 3,5-dimethylphenyl sulfonyls) Double sulfonyidiazomethanes classes such as diazomethane；P-methyl benzenesulfonic acid 2- nitrobenzene methyl esters, p-methyl benzenesulfonic acid 2,6- dinitrobenzene first Ester, toluenesulfonic acid nitrobenzene methyl esters, toluenesulfonic acid dinitrobenzene methyl esters, sulfonic acid nitrobenzene methyl esters, nitrophenylcarbonates methyl esters, carbonic acid The nitrobenzoyls radical derivative such as dinitrobenzene methyl esters；Pyrogallol triflate, pyrogallol front three benzene sulfonate, toluene Sulfonic acid benzene methyl, sulfonic acid benzene methyl, N- mesyloxy succinimide, N- trichloromethyl sulfonyloxy succinimide, N- The sulfonic acid esters such as phenylsulfonyloxy group maleimide, N- mesyloxy phthalimide；N- hydroxyl phthalyl The trifluoromethanesulfonic acids esters such as imines, N- hydroxynaphthylimide；Diphenyl iodine hexafluorophosphate, (4- methoxyphenyl) phenyl-iodide three Fluorine mesylate, bis- (to three-level butyl phenyl) iodine fluoroform sulphonates, triphenyl sulphur hexafluorophosphate, (4- methoxyphenyl) The salts such as diphenyl sulphur fluoroform sulphonate, (to three-level butyl phenyl) diphenyl sulphur fluoroform sulphonate；Styrax toluene The styraxes toluenesulfonic acid esters such as sulphonic acid ester, Alpha-Methyl styrax tosylate；Other diphenyl iodniums, triphenyl sulphur Salt, Arenediazonium salts, methyl phenyl carbonate etc..

Photoacid generator (C) can be used alone, and can also combine two or more use.Also, based on acid dissociation protecting group is contained Total usage amount of polyhydroxystyrene resin (A) be 100 parts by weight, the content of photoacid generator (C) is 0.3 parts by weight to 3 Parts by weight, preferably 0.4 parts by weight are to 2.8 parts by weight, more preferably 0.5 parts by weight to 2.5 parts by weight.

Solvent (D)

Solvent (D) is not particularly limited, as long as chemical amplification positive photosensitive resin composition institute user It can be used.Such as ester series solvent, non-ester series solvent etc..

Ester series solvent has, propylene-glycol monoalky lether acetic acid esters [such as propylene glycol methyl ether acetate (PGMEA) etc.], 3- second Oxygroup ethyl propionate, lactate (such as ethyl lactate etc.) etc..

In non-ester series solvent, there are ketone, polyvalent alcohols and its derivative, ring type ethers etc..

Ketone has, acetone, methyl ethyl ketone, cyclohexanone, first isoamyl ketone, 2-HEPTANONE etc..Polyvalent alcohols and its derivative have, second two Alcohol, propylene glycol, diethylene glycol or these monomethyl ether, single ether, single propyl ether, monobutyl ether, dimethyl ether, diethylene glycol dimethyl ether Or single phenyl ether etc..Ring type ethers has dioxanes etc..

Solvent can one or more be used in mixed way.

Chemical amplification positive photosensitive resin composition of the invention, to promote storage stability and ensuring to apply film property Stablize, organic solvent containing at least one selected from propylene-glycol monoalky lether acetic acid esters and 2-HEPTANONE to be preferred.

Total usage amount based on the polyhydroxystyrene resin (A) containing acid dissociation protecting group is 100 parts by weight, solvent (D) content is 200 parts by weight to 1200 parts by weight, preferably 200 parts by weight to 1100 parts by weight, more preferably 250 parts by weight To 1000 parts by weight.

Alkali compounds (E)

Alkali compounds (E) is as long as to have compatibility person to chemical amplification positive photosensitive resin composition, without spy Other limitation has such as the compound that Japanese Laid-Open Patent Publication 9-006001 bulletin is recorded.

It includes by formula (E-1) compound represented that alkali compounds (E), which is preferably:

N(A)_z(B)_3-zFormula (E-1)

In formula (E-1), A respectively independently indicates the naphthenic base that alkyl, carbon number that carbon number is 4 to 20 are 3 to 20, carbon number 6 To 20 phenyl or aralkyl；

B respectively independently indicates the alkyl that hydrogen atom or carbon number are 1 to 3；

Z indicates integer of 1 to 3.

Being preferably z by formula (E-1) compound represented is 2 or 3, and by the respective identical compound of the group represented by X.

As the alkyl of group A, if carbon number is not up to 4, it is difficult to promote the ageing stability of photoresist.Carbon number be in turn 5 with On, in particular 8 or more more preferably.Upper limit value is not particularly limited, from confirmation through when stablizing effect or commercially the point that obtains and Speech is 20 hereinafter, especially more preferably with 15 or less.In addition, base strength weakens when more than 20, drop the effect of storage stability It is low.

Alkyl is straight-chain, branched.Specifically, such as to be preferred positive decyl, n-octyl, n-pentyl.

As in the naphthenic base of group A, especially the naphthenic base of carbon number 4 to 8 can be by commercially obtaining, and is promoted through Shi Wending Property excellent result, more be suitble to.The cyclohexyl that carbon number is 6 is more preferably.

As the aralkyl of group A, the group as shown in formula (E-1a) can be enumerated:

- Q-P formula (E-1a)

In formula (E-1a), Q indicates alkylidene；P indicates aromatic hydrocarbyl.

As group P, phenyl, naphthalene etc. can be enumerated, is preferred with phenyl.As the alkylidene of group Q, carbon number is 1 or more , preferably 1 to 3.

As the aralkyl of group A, it is preferred with such as benzyl, phenylethyl etc..

It can be linear chain or branched chain person as the alkyl of group B.Especially it is preferred with methyl, ethyl.

Tertiary amine compounds are preferably by formula (E-1) compound represented.That is, if by formula (E-1) compound represented When with group B, group B is preferably alkyl.

By formula (E-1) compound represented, specifically, have such as three n-Decylamines, two n-octyl amine of methyl, tri-n-amyl amine, N, N- dicyclohexylmethylamine, tribenzyl amine etc..

One or more can be used to be used in mixed way for alkali compounds (E).Based on poly- containing acid dissociation protecting group Total usage amount of hydroxy styrenes resin (A) is 100 parts by weight, and the content of alkali compounds (E) is 0.03 parts by weight to 1.0 weights Measure part, preferably 0.04 parts by weight to 0.8 parts by weight, more preferably 0.05 parts by weight to 0.5 parts by weight.

When further including alkali compounds (E) in chemical amplification positive photosensitive resin composition, can further improve Chemical amplification positive photosensitive resin composition is formed by the taper angle of photoresist pattern.

Heterocyclic compound (F) with nitrogen-atoms

Chemical amplification positive photosensitive resin composition of the invention is selectively included the heterocycle with nitrogen-atoms Compound (F).The heterocyclic compound (F) with nitrogen-atoms may include, but are not limited to the heterocycle such as following formula (F-1) to formula (F-4) Compound:

In formula (F-1) into formula (F-4), G₁And G₂Separately represent hydrogen atom, acyl group or alkyl；H₁To H₉Respectively Independently represent hydrogen atom, hydroxyl, carboxylic acid group, sulfonic group, alkyl, amido, halogen atom or sulfydryl；W, v, q and s be independently Ground represents 0 to 3 integer；P and r separately represents 0 to 2 integer；And t and u separately represent 0 to 4 integer.

In formula (F-1) into formula (F-4), G₁With G₂Separately represent hydrogen atom, acyl group or alkyl.Specifically, G₁ With G₂It preferably can be the acyl group that carbon number is 2 to 4 or the alkyl that carbon number is 1 to 3.The acyl group that the carbon number is 2 to 4 may include but unlimited In acetyl group (acetyl group), propiono (propionyl group) or bytyry (butyryl group).The carbon number It may include, but are not limited to methyl, ethyl, isopropyl (i-propyl group) or n-propyl (n-propyl for 1 to 3 alkyl group)。

Above-mentioned H₁To H₉Separately represent hydrogen atom, hydroxyl, carboxylic acid group, sulfonic group, alkyl, amido, halogen atom Or sulfydryl.Specifically, working as H₁To H₉When for alkyl, H₁To H₉Preferably can be carbon number be 1 to 3 alkyl (such as: methyl, second Base, isopropyl or n-propyl)；Work as H₁To H₉When for halogen atom, the H₁To H₉It preferably can be chlorine atom, bromine atom or iodine atom. Work as H₁To H₉When for amido, and alkyl that the hydrogen atom that amido is bonded can be 1 to 3 by 1 or 2 carbon numbers (such as: methyl, second Base, isopropyl or n-propyl) it is replaced.In addition, H₁To H₉Be also possible to carbon number be 1 to 3 and with amido alkyl (such as: amine Ylmethyl, amido ethyl, amido isopropyl or amido n-propyl).

When above-mentioned w, v, p, q, r and s are greater than or equal to 2, a plurality of H₁、H₂、H₄、H₅、H₆And H₇It can be respectively identical Or different group.

The heterocyclic compound (F) with nitrogen-atoms may include, but are not limited to 6- methyl -8- hydroxyl quinoline (6-methyl- 8-hydroxyquinoline), 6- ethyl -8- hydroxyl quinoline (6-ethyl-8-hydroxyquinoline), 5- methyl -8- hydroxyl Base quinoline (5-methyl-8-hydroxyquinoline), 8- hydroxyl quinoline (8-hydroxyquinoline), 8- acetoxyl group Quinoline (8-acetyloxy quinoline), 4- hydroxypteridine (4-hydroxy pteridine), 2,4- dihydroxy pteridine (2, 4-dihydroxypteridine), 4- hydroxypteridine -2- sulfonic acid (4-hydroxypteridine-2-sulfonic acid), 2- ethyl -4- hydroxypteridine (2-ethyl-4-hydroxypteridine), 2- methyl -4- hydroxypteridine (2-methyl-4- Hydroxy pteridine), 2- amido -6,7- dimethyl -4- hydroxypteridine (2-Amino-6,7-dimethyl-4- Hydroxy pteridine), 1,10- Phen (1,10-phenanthroline), 5,6- dimethyl -1,10- neighbour's phenodiazine Luxuriant and rich with fragrance (5,6-dimethyl-1,10-phenanthroline), 3,8- dimethyl -1,10- Phen (3,8-dimethyl-1, 10-phenanthroline), 3,8- dihydroxy -1,10- Phen (3,8-dihydroxy-1,10- Phenanthroline), 5- carboxyl -1,10- Phen (5-carboxy-1,10-phenanthroline), 5,6- dihydroxy Base -1,10- Phen (5,6-dihydroxy-1,10-phenanthroline), 1,10- Phen -5- sulfonic acid (1, 10-phenanthroline-5-sulfonic acid), 4,4'- dimethyl -2,2'- bipyridyl (4,4'-dimethyl-2, 2'-bipyridyl), 2,2'- bipyridyl (2,2'-bipyridyl), 2,2'- bipyridyl -5- carboxylic acid (2,2'-bipyridyl- 5-carboxylic acid), the chloro- 2,2'- bipyridyl (5,5'-dichloro-2,2'-bipyridyl) of 5,5'- bis-, 3,3'- Dihydroxy -2,2'- bipyridyl (3,3'-dihydroxy-2,2'-bipyridyl), 3,3'- dimercapto -2,2'- bipyridyl (3, 3'-dimercapto-2,2'-bipyridyl) or any combination of above compound.The above-mentioned heterocyclic compound with nitrogen-atoms Object (F) can be used alone or mixing plural kinds of use.

Preferably, it can be 8- hydroxyl quinoline, 8- acetoxyl group quinoline, 4- hydroxyl that this, which has the heterocyclic compound (F) of nitrogen-atoms, Base pteridine, 2,4- dihydroxy pteridine, 1,10- Phen, 5,6- dimethyl -1,10- Phen, 2,2'- bipyridyl, 2, The combination of 2'- bipyridyl -5- carboxylic acid or above compound.

Total usage amount based on the polyhydroxystyrene resin (A) containing acid dissociation protecting group is 100 parts by weight, the tool The usage amount for having the heterocyclic compound (F) of nitrogen-atoms can be 0.01 parts by weight to 0.5 parts by weight, preferably can be for 0.01 parts by weight extremely 0.4 parts by weight, and more preferably can be 0.02 parts by weight to 0.3 parts by weight.

When chemical amplification positive photosensitive resin composition of the invention includes the heterocyclic compound (F) with nitrogen-atoms When, photoresist pattern obtained by chemical amplification positive photosensitive resin composition has more preferably adherence.

Additive (G)

In chemical amplification positive photosensitive resin composition, as long as not influencing effect of the invention, more can further it wrap Containing additive (G), additive (G) can be used alone one kind or use with it is a variety of, end see depending on actual needs.Illustrate additive below (G) particular content.

In chemical amplification positive photosensitive resin composition, to promote plasticity, it can also further contain polyethylene tree Rouge is as additive (G).As the specific example of polyvinyl resin, polyvinyl chloride, polystyrene, poly- hydroxy benzenes second can be enumerated Alkene, polystyrene formic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, gathers polyvinyl acetate Vinylphenol and these copolymer etc..Polyvinyl resin, based on glass transition temperature it is lower for, preferably polyvinyl methyl ether.

Also, being formed to be promoted using photosensitive resin composition in chemical amplification positive photosensitive resin composition Template and metal substrate followability, can also further contain then auxiliary agent as additive (G).

Furthermore in chemical amplification positive photosensitive resin composition, to promote coating, defoaming, equal levelling etc., Interfacial agent can further be contained as additive (G).As the specific example of interfacial agent, can enumerate BM-1000, BM-1100 (being BM Chmie corporation), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (being DIC corporation), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (being Sumitomo 3M corporation), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145 (being Asahi Glass corporation), SH-28PA, SH-190, SH-193, SZ-6032, The commercially available fluorine system interfacial agents such as SF-8428 (being Toray Silicone corporation), it is only non-limiting in these.

In addition, in chemical amplification positive photosensitive resin composition, to carry out the deliquescent fine tuning to developer solution, Acid, acid anhydrides or higher boiling solvent can further be contained as additive (G).

As acid and the specific example of acid anhydrides, acetic acid, propionic acid, n-butyric acie, isobutyric acid, positive valeric acid, isovaleric acid, benzene can be enumerated The monocarboxylic acids class such as formic acid, cinnamic acid；Lactic acid, 2- hydroxybutyric acid, 3-hydroxybutyrate, salicylic acid, m-hydroxybenzoic acid, para hydroxybenzene The hydroxyls list carboxylics such as formic acid, 2- hydroxyl cinnamic acid, 3- hydroxyl cinnamic acid, 4-Hydroxycinnamic Acid, 5- Hydroxy M Phthalic Acid, syringic acid Acids；Oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic two Formic acid, terephthalic acid (TPA), 1,2- cyclohexane dicarboxylic acid, 1,2,4- cyclohexanetricarboxylic acid, butane tetracarboxylic acid, trimellitic acid, benzene The polybasic carboxylic acids classes such as equal tetracid, pentamethylene tetrabasic carboxylic acid, butane tetracarboxylic acid, 1,2,5,8- naphthalene tetracarboxylic acid；Itaconic anhydride, succinic acid Acid anhydride, citraconic anhydride, laurylene succinic anhydride, tricarballylic acid's acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methyl tetrahydro are adjacent Phthalate anhydride, humic acid acid anhydride, 1,2,3,4- butane tetracarboxylic acid anhydrides, pentamethylene tetracarboxylic dianhydride, phthalic anhydride, benzene equal four The double trimellitic anhydrides of acid anhydrides, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol, glycerine join trimellitic anhydride Equal acid anhydrides；Deng.

Also, the specific example as higher boiling solvent, can enumerate N-METHYLFORMAMIDE, n,N-Dimethylformamide, N- first Yl carboxylic acid anilides, N- methylacetamide, DMAC N,N' dimethyl acetamide, N- methylpyrrole pyridine ketone, dimethyl sulfoxide, benzyl second Ether, two hexyl ethers, pentanedione, different Buddhist ketone, caproic acid, octanoic acid, 1- octanol, 1 nonyl alcohol, benzyl alcohol, phenylmethyl acetate, benzoic acid Ethyl ester, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propene carbonate, phenyl Sai Lusu acetic acid esters Deng.

Also, to promote sensitivity, can also further make containing sensitizer in chemical amplification positive photosensitive resin composition For additive (G).

There is no particular restriction for the manufacturing method of chemical amplification positive photosensitive resin composition, can by it is above-mentioned it is each at Divide and is made with common method mixing, stirring.As device workable when mixing, stirring by above-mentioned each ingredient, can enumerate Dissolving machine, homogenizer, three-roll mill etc..After evenly mixing by above-mentioned each ingredient, gained mixture can also further be utilized Sieve, molecular filter etc. are filtered.

The present invention more provides a kind of forming method of photoresist pattern, below to the forming method of photoresist pattern of the invention into Row explanation.

Firstly, chemical amplification positive photosensitive resin composition of the invention is coated on substrate, shape with rotator etc. At film.

Substrate is preferred so that the glass substrate of silicon fiml is arranged.The formation of silicon fiml, usually using uncrystalline silicon, system LCD's Field is preferred with low-temperature poly-silicon etc..Also, can be used 300mm × 400mm or more large substrate, especially 550mm × 650mm with On large substrate.

Then, heat the substrate to form this film (pre-baked) at such as 90~140 DEG C, removal remains molten Agent forms photoresist envelope.Heat the method for (pre-baked), to have the neighbouring baking in gap between heating plate and substrate (Proximity Bake) heating method is preferred.

Then, using the light of the both sides of the mask pattern for the mask pattern and liquid-crystal display section for describing integrated circuit Cover carries out selective exposure to above-mentioned photoresist envelope.

To form fine pattern, light source as used herein is to use i line (365nm) to be preferred.Also, exposure uses herein Exposure technology with NA be 0.3 hereinafter, preferably 0.2 hereinafter, more preferably 0.15 low NA condition below exposure technology.Pass through Using exposure technology under the conditions of low NA, primary exposure area can be expanded, production capacity can be improved.

Then, the photoresist envelope after selectivity exposure is heated and (is baked after exposure).The method baked after exposure has: adding There is the neighbouring baking (Proximity Bake) in gap between hot plate and substrate and do not have the direct baking (Direct in gap The methods of Bake).Wherein, the diffusion effect baked after being exposed in order not to cause the warpage of substrate preferably carries out neighbouring dry The method of direct baking is carried out after roasting again.Herein, heating temperature is 90~150 DEG C, more preferably with 100~140 DEG C.

Then, using developer solution, such as the aqueous alkali of 1~10 mass % tetramethyl ammonium hydroxide aqueous solution, to above-mentioned Photoresist envelope after baking after exposure carries out development treatment, dissolution removal exposed portion, while integrated circuit is formed on substrate Photoresist pattern, the photoresist pattern with liquid-crystal display section.

Then, by cleaning the developer solution for remaining in photoresist patterned surfaces with flushing liquors such as pure water, photoresist figure can be formed Case.

In carrying out the above-mentioned process selectively exposed, describe 2.0 μm of formation photoresist pattern light shields below to use The light shield of the both sides of pattern and the formation photoresist pattern mask pattern more than 2.0 μm is more suitble to as above-mentioned light shield.

Chemical amplification positive photosensitive resin composition of the invention can get faithful reproduction light because it is linear excellent The coarse patterns of cover pattern and the photoresist pattern of fine pattern.Therefore, 2.0 μm of pattern dimension or less can be formed on substrate simultaneously Integrated circuit photoresist pattern, with liquid-crystal display section photoresist pattern more than 2.0 μm.

The synthesis example of polyhydroxystyrene resin (A) containing acid dissociation protecting group

Illustrate the synthesis example A-1 to A-6 and ratio of the polyhydroxystyrene resin (A) containing acid dissociation protecting group below Compared with synthesis example A ' -1:

Synthesis example A-1

680 parts by weight are added in the polyhydroxystyrene resin that the weight average molecular weight of 120 parts by weight is 13,000 After being dissolved in n,N-dimethylacetamide, the chloro- Ethoxyethane of the 1- of 42.3 parts by weight is added in four cervical vertebra bottles, is slowly stirred Above-mentioned mixed solution is mixed to being completely dissolved.Then, the speed to be added dropwise within 30 minutes or so time is leaked through liquid feeding The triethylamine of 78.8 parts by weight is added dropwise in bucket, and carries out reaction 3 hours.After reaction, it is added relative to above-mentioned mixed solution Total amount be 20 times amount pure water, make containing 1- ethoxyethyl group as acid dissociation protecting group polyhydroxystyrene resin analyse Out, after above-mentioned precipitate being cleaned with pure water, be dehydrated, being dry, i.e. the hydrogen atom Replacement rate of acquisition phenolic hydroxyl group is 39mol% Containing 1- ethoxyethyl group as the polyhydroxystyrene resin (A-1) of acid dissociation protecting group.

Synthesis example A-2 to A-3

Synthesis example A-2 to A-3 is to be prepared with identical with synthesis example A-1 process, and it is different in: changing institute The weight average molecular weight of the polyhydroxystyrene resin used and its hydrogen atom Replacement rate (as shown in table 1) of phenolic hydroxyl group.

Synthesis example A-4

680 parts by weight are added in the polyhydroxystyrene resin that the weight average molecular weight of 120 parts by weight is 13,000 After being dissolved in n,N-dimethylacetamide, the di-tert-butyl dicarbonate of 85 parts by weight is added in four cervical vertebra bottles, is slowly stirred Above-mentioned mixed solution is to being completely dissolved.Then, the speed to be added dropwise within 15 minutes or so time, through addition funnel The triethylamine of 59 parts by weight is added dropwise, and carries out reaction 3 hours.After reaction, it is added relative to the total of above-mentioned mixed solution Amount is the pure water of 20 times of amounts, and the polyhydroxystyrene resin containing tert-butoxycarbonyl as acid dissociation protecting group is precipitated, After above-mentioned precipitate is cleaned with pure water, is dehydrated, is dry, i.e. the hydrogen atom Replacement rate of acquisition phenolic hydroxyl group is 39mol%'s Containing tert-butoxycarbonyl as the polyhydroxystyrene resin (A-4) of acid dissociation protecting group.

Synthesis example A-5 to A-6

Synthesis example A-5 to A-6 is to be prepared with identical with synthesis example A-1 process, and it is different in: changing institute The weight average molecular weight of the polyhydroxystyrene resin used and its hydrogen atom Replacement rate (as shown in table 1) of phenolic hydroxyl group.

Compare synthesis example A ' -1

In 1000 milliliters of the volume for having cooling tube of three cervical vertebra bottles, the 4-Vinyl phenol of 120 parts by weight is added After dissolving in the tetrahydrofuran of 480 parts by weight, above-mentioned mixed solution is slowly stirred to dissolution.Then, by 2,2 '-azos pair- 2- isopropyl butyronitrile (AIBN) is added in three cervical vertebra bottles to carry out polymerization reaction, and the reaction temperature of entire polymerization process maintains 75 ℃.After the completion of polymerization, polymerizate is taken out, and solvent is sloughed from four cervical vertebra bottles, can obtain and not have acid dissociation protection The polyhydroxystyrene resin (A ' -1) of base, weight average molecular weight 13,000.

[table 1]

The embodiment of chemical amplification positive photosensitive resin composition

Illustrate the embodiment 1 to 13 and comparative example 1 to 3 of chemical amplification positive photosensitive resin composition below:

Embodiment 1

By the polyhydroxystyrene resin containing acid dissociation protecting group of resulting 100 parts by weight of above-mentioned synthesis example A-1 (A-1), 350 weights are added in the photoacid generator (C-1) of the 9- decene nitrile (referred to as B-1) of 0.03 parts by weight and 2.5 parts by weight Measure part propylene glycol methyl ether acetate (referred to as D-1) after, with swing-out stirrer, dissolved mixing, i.e., it is modulated and Chemical amplification positive photosensitive resin composition, the chemical amplification positive photosensitive resin composition is with following each Evaluation of measuring mode is evaluated, and acquired results are as shown in table 2.

Embodiment 2 is to embodiment 13

Embodiment 2 to embodiment 13 is made using with the chemical amplification positive photosensitive resin composition of embodiment 1 The identical operating method of method, the difference is that embodiment 2 to embodiment 13 is to change chemical amplification positive photonasty tree The type and usage amount of raw material in fat composition, formula and following evaluation result are as shown in table 2 or table 3.

Comparative example 1 is to comparative example 3

Comparative example 1 to comparative example 3 is using the chemical amplification positive photosensitive resin composition production side with embodiment 1 The identical operating method of method, the difference is that comparative example 1 to comparative example 3 is to change chemical amplification positive photoresist group At the type and usage amount of raw material in object, formula and following evaluation result are as shown in table 3.

Compound corresponding to label is as follows in table 2~3.

[table 2]

[table 3]

Evaluation method

Adherence

Using light blockage coating device (device name: chemical industry limited liability company system is answered in TR36000, Tokyo), will implement After the chemical amplification positive photosensitive resin composition of example and comparative example is coated on ito substrate (100mm × 100mm), Pre-baked, the photoresist of 1.5 μm of film thickness of formation is carried out by gap about 1mm close to heating with 110 DEG C, 90 seconds heating conditions Envelope.Then, using i line exposing device (device name: FX-702J, Nikon Corporation system, NA=0.14) and L&S (line and sky Between) photoresist pattern test figure light shield, with 100mJ/cm²Ultraviolet light pre-baked film is exposed.After exposure, with 110 DEG C, 90 seconds conditions bake (PEB) after being exposed by the gap 0.5mm close to heating.Then, using 23 DEG C, 2.38 Quality % tetramethylammonium hydroxide (TMAH) aqueous solution carries out 41 seconds development treatments, exposed on glass substrate to remove Part film.Finally, with the flushing of pure water progress 15 seconds, and developing pattern is recorded in the line that can develop on glass substrate It is wide.The evaluation criteria for the line width that can develop is as follows, wherein the line width that can develop is smaller, indicates that adherence when development is got over Good, specific evaluation criterion is as follows:

◎: line width≤5 μm that can develop

Zero: 5 μm < line width≤10 μm that can develop

△: 10 μm < line width≤20 μm that can develop

X: line width > 20 μm that can develop

Taper angle

Fig. 1 is please referred to, Fig. 1 is the schematic diagram for measuring the taper angle of photoresist pattern.Photoresist after above-mentioned development is carried out 130 DEG C, 150 seconds rear roasting, then, observe section shape；Wherein, taper angle 1 is to the angle between substrate 3 and photoresist pattern 2 (angle shown in θ in figure), specific evaluation criterion is as follows:

◎: 80 degree≤| taper angle |≤90 degree

Zero: 70 degree≤| taper angle | 80 degree or 90 degree < of < | taper angle |≤100 degree

△: 60 degree≤| taper angle | 70 degree or 100 degree < of < | taper angle |≤110 degree

X:| taper angle | 60 degree of < or | taper angle | > 110 degree

Evaluation result

It is learnt by table 2, table 3, and includes the polyhydroxystyrene resin (A) containing acid dissociation protecting group and single insatiable hunger Photoresist pattern phase obtained by chemical amplification positive photosensitive resin composition (embodiment 1-13) with nitrile compound (B) Than not including the chemical amplification positive photoresist group of the polyhydroxystyrene resin (A) containing acid dissociation protecting group At object (comparative example 1,3), taper angle evaluation is bad；And even if include the polycarboxylated styrene tree containing acid dissociation protecting group Rouge (A), and do not include the chemical amplification positive photosensitive resin composition of single unsaturated nitrile compound (B) of tool specific structure (comparative example 2), adherence, taper angle evaluation are all bad.

In addition, when in chemical amplification positive photosensitive resin composition, the carbon atom of single unsaturated nitrile compound (B) When number is 6~30 (embodiment 1~11,13), (embodiment when the carbon atomicity compared to single unsaturated nitrile compound (B) is 5 12), adherence, taper angle are evaluated more preferably.

In addition, further including alkali compounds (E) (embodiment 4- when in chemical amplification positive photosensitive resin composition 8, when 11,13), the evaluation of taper angle is performed better.

In addition, further including the heterocyclic compound with nitrogen-atoms when in chemical amplification positive photosensitive resin composition (F) when (embodiment 5-9,11,13), the evaluation of adherence is performed better.

In conclusion chemical amplification positive photosensitive resin composition of the invention is protected because containing containing acid dissociation The polyhydroxystyrene resin (A) of base and single unsaturated nitrile compound (B), therefore adherence can be improved and taper angle is bad The problem of.

On the other hand, if in chemical amplification positive photosensitive resin composition of the invention, single unsaturated nitrile compound (B) when carbon atomicity is 6~30, adherence, taper angle evaluation are more preferably.

On the other hand, if more containing alkali compounds in chemical amplification positive photosensitive resin composition of the invention (E) when, the evaluation of taper angle is performed better；And if in chemical amplification positive photosensitive resin composition of the invention When more containing heterocyclic compound (F) with nitrogen-atoms, the evaluation of adherence is performed better.

Although the present invention is disclosed as above with embodiment, however, it is not to limit the invention, any technical field In technical staff, without departing from the spirit and scope of the present invention, when can make a little change and retouching, therefore guarantor of the invention Subject to shield range ought be defined depending on claim.

Claims

1. a kind of chemical amplification positive photosensitive resin composition characterized by comprising

Polyhydroxystyrene resin (A) containing acid dissociation protecting group；

Single unsaturated nitrile compound (B)；

Photoacid generator (C)；And

Solvent (D).

2. chemical amplification positive photosensitive resin composition according to claim 1, wherein the list unsaturated nitrile The carbon atomicity for closing object (B) is 6~30.

3. chemical amplification positive photosensitive resin composition according to claim 1, wherein the list unsaturated nitrile It closes object (B) and is selected from decene nitrile, decene dintrile, endecatylene nitrile, dodecylene nitrile, tridecylene nitrile, tetradecene nitrile, 16 carbon Alkene nitrile, hexadecene dintrile, octadecene nitrile, octadecene dintrile and two dodecylene nitriles compound composed by group At least one of.

4. chemical amplification positive photosensitive resin composition according to claim 1, wherein further including alkali compounds (E)。

5. chemical amplification positive photosensitive resin composition according to claim 4, wherein the alkali compounds (E) Including by formula (E-1) compound represented:

N(A)_z(B)_3-zFormula (E-1)

In formula (E-1), the naphthenic base, carbon number that A respectively independently indicates that alkyl, carbon number that carbon number is 4 to 20 are 3 to 20 are 6 to 20 Phenyl or aralkyl；

Z indicates integer of 1 to 3.

6. chemical amplification positive photosensitive resin composition according to claim 1, further includes:

Heterocyclic compound (F) with nitrogen-atoms, selected from as composed by following formula (F-1) to formula (F-4) compound represented Group:

In formula (F-1) into formula (F-4), G₁And G₂Separately represent hydrogen atom, acyl group or alkyl；H₁To H₉Separately Represent hydrogen atom, hydroxyl, carboxylic acid group, sulfonic group, alkyl, amido, halogen atom or sulfydryl；W, v, q and s are separately represented 0 to 3 integer；P and r separately represents 0 to 2 integer；And t and u separately represent 0 to 4 integer.

7. chemical amplification positive photosensitive resin composition according to claim 1, wherein containing acidolysis based on described Total usage amount of polyhydroxystyrene resin (A) from property protecting group is 100 parts by weight, the list unsaturated nitrile compound (B) Content be 0.03 parts by weight to 1.0 parts by weight, the content of the photoacid generator (C) is 0.3 parts by weight to 3 parts by weight, institute The content for stating solvent (D) is 200 parts by weight to 1200 parts by weight.

8. chemical amplification positive photosensitive resin composition according to claim 4, wherein containing acidolysis based on described Total usage amount of polyhydroxystyrene resin (A) from property protecting group is 100 parts by weight, the content of the alkali compounds (E) For 0.03 parts by weight to 1.0 parts by weight.

9. chemical amplification positive photosensitive resin composition according to claim 6, wherein containing acidolysis based on described Total usage amount of polyhydroxystyrene resin (A) from property protecting group is 100 parts by weight, the heterocyclic compound with nitrogen-atoms The content of object (F) is 0.01 parts by weight to 0.5 parts by weight.

10. a kind of forming method of photoresist pattern, comprising:

Chemical amplification positive photosensitive resin composition according to any one of claim 1 to 9 is coated on substrate Process.

11. a kind of photoresist pattern is formed by the forming method of photoresist pattern according to claim 10.

12. a kind of electronic device includes photoresist pattern according to claim 10.