CN101553758A - Pattern forming method and photosensitive resin composition used therefor - Google Patents

Pattern forming method and photosensitive resin composition used therefor Download PDF

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Publication number
CN101553758A
CN101553758A CNA2007800394213A CN200780039421A CN101553758A CN 101553758 A CN101553758 A CN 101553758A CN A2007800394213 A CNA2007800394213 A CN A2007800394213A CN 200780039421 A CN200780039421 A CN 200780039421A CN 101553758 A CN101553758 A CN 101553758A
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pattern
cosolvent
mixed solvent
polymer combination
photosensitive polymer
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CN101553758B (en
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河户俊二
远山宜亮
谷口克人
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Merck Patent GmbH
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AZ Electronic Materials Japan Co Ltd
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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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G03F7/16—Coating processes; Apparatus therefor

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a photosensitive resin composition which enables to improve coatability and pattern shapes formed therewith. Also disclosed is a pattern forming method using such a photosensitive resin composition. The photosensitive resin composition contains an alkali-soluble resin, a sensitizing agent, and a mixed solvent. The mixed solvent contains propylene glycol monomethyl ether acetate and a cosolvent having a vapor pressure of not more than 150 Pa at 20 DEG C. This composition is preferably used in slit coating methods.

Description

The formation method of pattern and employed photosensitive polymer combination thereof
Technical field
The present invention relates to photo-corrosion-resisting agent composition.The present invention be more particularly directed to be applicable to the photo-corrosion-resisting agent composition that applies by slit die.
Background technology
LCD before forming is with the photoresist of driving circuit pattern, and normally by after the glass central part ejection photosensitive polymer combination and the spin coated of spinning, it is dry and make to carry out prebake again.Yet owing to the maximization of substrate, the minimizing of dosage against corrosion, coating method is also different, also will use after carrying out slit coating, makes the method for its spin rotation and prebake drying.And,, carry out drying under reduced pressure and carry out the manufacture method of prebake drying if, then will adopt after carrying out slit coating owing to the further maximization of substrate requires to make the spin rotation difficulty that becomes.
The purpose of rotation of spinning behind the slit coating be make film in contained solvent partly evaporate and make the homogenization of filming.Therefore, adopt the method for the rotation of behind slit coating, spinning, can guarantee the homogeneity that applies by the spin rotation.And adopt the method for behind slit coating, carrying out drying under reduced pressure, owing to can not make the homogenization of filming by the spin rotation, so filming behind the slit coating must be homogeneous.But, according to present inventors' research, used in the past photosensitive polymer combination is directly used, just carry out filming behind the slit coating and also be difficult to the homogeneity that reaches enough.And, after in the drying under reduced pressure process of carrying out, the vestige that also occurs the chuck of the substrate after the fixing coating and register pin etc. easily remains in the problem of coated surface.
In addition, the condition of the drying under reduced pressure that carries out behind slit coating has multiple, and great majority are to adopt at ambient temperature basically, through about about 30 seconds from the atmospheric pressure rapid decompression of the about 101kPa method of about 20Pa extremely.Owing to adopt this strict drying under reduced pressure condition, thereby must regulate the degree of drying of filming.If the degree of drying of filming is improper, then can produce big problem aspect pattern form and the screening characteristics, will become the main cause that causes various troubles.
As the solvent that uses in this photosensitive polymer combination, the vapor pressure of (below be also referred to as PGMEA) is about 500Pa under 20 ℃/1 atmospheric pressure because normally used propylene glycol methyl ether acetate, is very easy to evaporation when drying under reduced pressure.As a result, the film coated surface of PGMEA after the coating evaporated rapidly, forms dry overlay film in surperficial adjacent domain, hindered the evaporation of the inner PGMEA that films.If form pattern with this resist film, then owing to resist film surface adjacent domain is difficult to develop, and inner development easily, so pattern form becomes reverse tapered shapes (being also referred to as T-top), after have the pattern bight residual when curing, it will become the main cause of peeling off defective, and, because the inside drying of resist pattern is insufficient, thereby etch resistance is also good inadequately, it will become the inhomogenous main causes such as metal line that cause with this resist pattern formation.
In addition, forming with positive photoresist in the process of pattern, as a rule known when behind end exposure, resist film being developed, emulsion and resin carried out the azo bonding when unexposed portion contacted with developer solution, reduce its dissolubility, can make exposed portion and unexposed portion produce difference thus for alkaline developer.Carry out in the method for drying under reduced pressure again after photosensitive composite before using carries out slit coating, because the drying of film coated surface, make the inner relative difficult of surface ratio of unexposed portion be dissolved in alkaline developer, so there is the tendency that makes apparent contrast become excessive.In order to address this is that, can enumerate and for example not add the low-molecular-weight resin composition reactive high that is called contrast-enhancing agents with emulsion, perhaps reduce the amount of emulsion.But, adopt this method, though for the shape of pattern, can confirm the effect that has some improvement, can produce the quantity not sufficient of emulsion and cause the pattern width inequality, and owing to there not being contrast-enhancing agents to make problems such as actual contrast reduction.
On the other hand, when the coating photosensitive polymer combination forms etchant resist,, studied multiple solvent has been mixed in order to suppress to apply spot.For example, in patent documentation 1, disclose and adopted diglycol dialkyl ether, 3-ethoxyl ethyl propionate, alkyl acetate and lactic acid alkyl ester photosensitive polymer combination as solvent.The purpose of the photosensitive polymer combination of record is horizontal stripe spot, vertical stripe spot and whole the spot of going up no solid shape of substrate etc. that improve in the slit coating in this patent documentation 1.And velocity of evaporation has been considered in the combination of this solvent, but this velocity of evaporation is the velocity of evaporation in when coating, does not consider the velocity of evaporation in the process such as drying under reduced pressure.Therefore, known to present inventors, aspect the problem when solving above-mentioned drying under reduced pressure, also has improved space.
In addition, in patent documentation 2, put down in writing the photosensitive polymer combination that contains benzylalcohol.Benzylalcohol used herein is blended in order to improve the coating spot in the main solvent such as propylene glycol methyl ether acetate and uses.Yet, as the coating method in this patent documentation, be to be described specially at the method that adopts spin-coating method, for the problem in the above-mentioned slit coating that comprises drying under reduced pressure without any explanation.
Patent documentation 1: TOHKEMY 2006-171670 communique
Patent documentation 2: international monopoly discloses pamphlet No. 2004/095142
Summary of the invention
As mentioned above, research according to present inventors, contain the photosensitive polymer combination of normally used propylene glycol methyl ether acetate if adopt as solvent, also has improved space aspect coating spot when coating and the coating homogeneity, and because film coated surface is than inner easy drying, make pattern form become back taper, and defective and excessive contrast are peeled off in existence.Therefore, the method that need seek to address these problems.
Pattern formation method of the present invention is characterised in that and comprises:
Photosensitive polymer combination is coated on by the slit die coating process its formation is filmed, above-mentioned photosensitive polymer combination contains alkali soluble resin, emulsion and mixed solvent, and above-mentioned mixed solvent contains propylene glycol methyl ether acetate and is cosolvent below the 150Pa in 1 atmospheric pressure, 20 ℃ of following vapor pressures;
Formed filming carried out drying under reduced pressure;
Proceed heat drying, remove at least a portion solvent with evaporation;
Carry out image exposure by required pattern;
Develop and make it form pattern;
Pattern after developing heated make its curing.
In addition, slit die of the present invention is coated with the application photosensitive polymer combination and is characterised in that and contains alkali soluble resin, emulsion and mixed solvent, and above-mentioned mixed solvent contains propylene glycol methyl ether acetate and is cosolvent below the 150Pa in 1 atmospheric pressure, 20 ℃ of following vapor pressures.
According to the present invention, the coating spot in the time of can improving coating and the inhomogeneity of coating, and can make formed pattern form become preferred taper, and can improve the inhomogeneity of peeling off defective and live width.Pattern form has improved, but also the unequal problem of the pattern width that method produced of the amount of the minimizing emulsion of carrying out before not bringing and contrast-enhancing agents etc.
Description of drawings
Fig. 1 is the schematic cross-section of the resist pattern after developing.
Description of symbols
1: substrate
2: the resist pattern after the development
Embodiment
The photosensitive polymer combination that uses in the pattern formation method of the present invention contains alkali soluble resin, emulsion and mixed solvent as essential composition.The photosensitive polymer combination that uses in the pattern formation method of the present invention can be adjusted the composition of photosensitive polymer combination according to purposes of formed pattern etc., and any one all can positivity or negativity.
Here, mixed solvent comprises propylene glycol methyl ether acetate and cosolvent.Here, as cosolvent, adopting in 1 atmospheric pressure, 20 ℃ of vapor pressures of measuring down is below the 150Pa, is preferably the following cosolvent of 100Pa.In addition, the lower limit for the cosolvent vapor pressure has no particular limits, and in 1 atmospheric pressure, 20 ℃ of vapor pressures of measuring down, is generally more than the 5Pa, is preferably more than the 10Pa, more preferably more than the 15Pa.When this scope of the steaming pressure ratio of cosolvent also will be hanged down, then when drying under reduced pressure, be difficult to regulate drying condition, make by the abundant drying of drying under reduced pressure and the prebake of carrying out in succession, thereby make residual solvent in the resist film, so need be careful.Cosolvent is because satisfy this condition, thereby can suitably select according to purposes, coating or the drying condition etc. of the kind of other contained in photosensitive polymer combination solid constituents, photosensitive polymer combination.
As the preferred solvent of this cosolvent, can enumerate alcohols, ester class, ethers, gylcol ether etc.Object lesson as preferred cosolvent, can enumerate and be selected from benzylalcohol, the ethylene glycol butyl ether acetic acid esters, more particularly, ethylene glycol just-/different-/secondary-/tert-butyl ether acetic acid ester, propylene glycol, propylene-glycol diacetate, propylene-glycol monoalky lether (carbon number of alkyl is 4～5), dipropylene glycol dialkyl ether (carbon number of alkyl is 1～5), dipropylene glycol monoalky lether (carbon number of alkyl is 1～5), diglycol dialkyl ether (carbon number of alkyl is 2～5), diglycol monotertiary alkyl ether (carbon number of alkyl is 1～5), the 3-ethoxyl ethyl propionate, 3-methoxyl-3-methyl butyl acetic acid esters, 3-methoxyl-3-methyl butanol, cosolvent in the group that butyl lactate and their potpourri constitute.
In addition, though benzylalcohol is one of preferred as cosolvent, can also constitute screening characteristics excellent solvent more by the mixed solvent that further is combined into three components with other cosolvent.As the mixed solvent of this preferred three components, can enumerate for example mixed solvent of PGMEA, benzylalcohol and ethylene glycol n-butyl ether acetic acid ester.PGMEA compares with above-mentioned three component mixed solvents with the bi-component mixed solvent of benzylalcohol, exists screening characteristics to want a little bit poorer tendency.
In the present invention, this cosolvent and PGMEA are mixed into mixed solvent.Mixture ratio to mixed solvent has no particular limits, and the content of preferred cosolvent is 5～70 weight % based on the weight of whole mixed solvents, is preferably 5～60 weight %.At this moment, using the volatility height, promptly under the situation of the cosolvent that vapor pressure is high, the content of preferred cosolvent is more relatively.Remainder only is PGMEA preferably, but in the scope of not damaging effect of the present invention, can also contains other solvents, for example surpasses the solvent of 150Pa in 1 atmospheric pressure, 20 ℃ of vapor pressures of measuring down.In addition, in the present invention, mixed solvent might not with PGMEA together the state of solvent use, can also be when the preparation of photosensitive polymer combination, add PGMEA and cosolvent respectively and in composition, mix.
In addition, when using when 1 atmospheric pressure, 20 ℃ of vapor pressures of measuring down surpass the cosolvent of 150Pa and mixed solvent that PGMEA combines, though can find the situation that the coating performance of photosensitive polymer combination increases, have the situation of film dry tack free when being difficult to fully suppress drying under reduced pressure.And because the film dry tack free, reduce so be difficult to produce film when developing, residual film ratio makes pattern form become back taper easily near 100%.By contrast, with the vapor pressure be solvent below the 150Pa as cosolvent, when prebake, be difficult to drying.Therefore, during adding, former spin-coating method finds the reduction of residual film ratio, even in the case, even when making up, under the situation of rapid decompression, also can suppress the drying on film surface, and can guarantee residual film ratio with drying under reduced pressure.
As operable alkali soluble resin in the pattern formation method of the present invention, can use previously known any resin.Particularly, can enumerate novolac resin, polymkeric substance, acrylic polymers, silanol polysiloxane, polyimide etc. with silazane structure.Wherein, phenol phenolics such as preferred phenolic resin, particularly cresol novolac resin, xylenol phenolics.
Here so-called phenol phenolics is meant the aldehyde condensation polymer such as at least a and formaldehyde of phenols and the novolac type phenol resin that obtains.
As the employed phenols of this phenol phenolics of preparation, can enumerate for example orthoresol, cresols such as paracresol and metacresol class, 3, the 5-xylenol, 2, the 5-xylenol, 2, the 3-xylenol, 3, dimethyl benzene phenols such as 4-xylenol, 2,3, the 4-pseudocuminol, 2,3, the 5-pseudocuminol, 2,4, the 5-pseudocuminol, 3,4, trimethylbenzene phenols such as 5-pseudocuminol, the 2-tert-butyl phenol, the 3-tert-butyl phenol, tert-butyl phenols such as 4-tert-butyl phenol, the 2-metoxyphenol, the 3-metoxyphenol, the 4-metoxyphenol, 2, the 3-syringol, 2, the 5-syringol, 3, methoxybenzene phenols such as 5-syringol, the 2-ethyl-phenol, the 3-ethyl-phenol, the 4-ethyl-phenol, 2, the 3-diethyl phenol, 3, the 5-diethyl phenol, 2,3,5-triethyl phenol, 3,4, ethylbenzene phenols such as 5-triethyl phenol, o-chlorphenol, m-Chlorophenol, parachlorophenol, 2, chlorobenzene phenols such as 3-chlorophenesic acid, resorcinol, the 2-methylresorcinol, cresorcinol, resorcinol classes such as oreinol diphenol, catechols such as 5-methyl pyrocatechol, pyrogallol classes such as 5-methyl pyrogallol, bisphenol-A, B, C, D, E, bisphenols such as F, 2, methylolation cresols classes such as 6-dihydroxymethyl p-methyl phenol, alpha-Naphthol, aphthols such as betanaphthol etc.They can use separately or with multiple potpourri.
In addition, as aldehydes, except formaldehyde, can enumerate salicylide, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxy benzaldehyde, chloroacetaldehyde etc., they can use separately or with multiple potpourri.
Content to alkali soluble resin has no particular limits, and the general assembly (TW) based on photosensitive polymer combination is 5～25 weight % usually, is preferably 7～20 weight %.If also littler than this scope, then, must apply very thick composition in order to make final resist film reach certain thickness, so cause inner the flowing of filming easily, the situation of coating spot can appear producing.On the other hand,, then very thin composition must be applied, the imperfect situation of homogeneity of film thickness can be occurred if the content of resin is more taller than this scope.Therefore, when the content of resin drops on beyond the above-mentioned scope, should be noted that.
In addition,, can from normally used emulsion, at random select,, can enumerate the emulsion that contains the quinone diazido as preferably as the emulsion of using in the pattern formation method of the present invention.As this emulsion, can enumerate with naphthoquinones two nitrine sulfonic acid chlorides or benzoquinones two nitrine sulfonic acid chlorides etc. with have the compound that can carry out the low molecular compound of functional group of condensation reaction or macromolecular compound reaction with these chloride things and obtain.Here, as can with the functional group of chloride thing condensation, can enumerate hydroxyl, amino etc., and the hydroxyl particularly suitable.As hydroxyl can with the compound of chloride thing condensation, can enumerate for example p-dihydroxy-benzene, resorcinol, 2, the 4-hydroxy benzophenone, 2,3,4-trihydroxy benzophenone, 2,4,6-trihydroxy benzophenone, 2,4,4 '-trihydroxy benzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,2 ', 3,4, hydroxy benzophenone classes such as 6 '-pentahydroxybenzophenone, two (2, the 4-dihydroxy phenyl) methane, two (2,3,4-trihydroxy phenyl) methane, hydroxy phenyl alkanes such as two (2, the 4-dihydroxy phenyl) propane, 4,4 '; 3 ", 4 "-tetrahydroxy-3,5; 3 ', 5 '-tetramethyl triphenyl methane; 4,4 '; 2 ", 3 ", 4 "-penta hydroxy group-3,5, hydroxyl triphenylmethanes such as 3 ', 5 '-tetramethyl triphenyl methane etc.They can use separately, and also can be used in combination.
In addition, as sulfonic acid chlorides such as naphthoquinones two nitrine sulfonic acid chlorides or benzoquinones two nitrine sulfonic acid chlorides, for example preferably can enumerate 1,2-naphthoquinones two nitrine-5-sulfonic acid chloride, 1,2-naphthoquinones two nitrine-4-sulfonic acid chloride etc.The combined amount that contains the emulsion of quinone diazido, per 100 weight portion alkali soluble resins are generally 5～50 weight portions, are preferably 10～40 weight portions.If also lack than this amount, the situation of enough susceptibilitys then can appear can not obtaining as photosensitive polymer combination, on the other hand,, then can produce the problem of separating out composition if also more than this amount, therefore should be noted that.
The photosensitive polymer combination that uses in the pattern formation method of the present invention contains above-mentioned mixed solvent, alkali soluble resin, emulsion as essential composition, and can further contain surfactant.The purpose of surfactant is the homogeneity that keeps photosensitive polymer combination, improves screening characteristics etc.Particularly when being coated on photosensitive polymer combination on the base material, can producing flakey texture (hereinafter referred to as " scale spot ") on the surface, and, can suppress this scale spot by in photosensitive polymer combination of the present invention, using surfactant.Especially preferably use nonionic class surfactant in the photosensitive polymer combination of the present invention.As nonionic class surfactant, comprise fluorine class surfactant, siloxane type surfactants, hydrocarbon-surfactant etc., especially preferably use fluorine class surfactant.The combined amount of these surfactants with respect to the total amount of 1 weight portion alkali soluble resin and emulsion, is added 200～10000ppm usually.If the content of surfactant is too much, then can cause problems such as poor visualization, therefore should be noted that.
The photosensitive polymer combination that uses in the pattern formation method of the present invention as required, can also further contain adjuvant, for example bonding agents such as contrast-enhancing agents, epoxy compounds or silicon-containing compound.These adjuvants can be selected from previously known any adjuvant in not damaging effective scope of the present invention.
The photosensitive polymer combination that uses in the pattern formation method of the present invention is used for the coating undertaken by slit coating method (being also referred to as slit die coating process or irrotationality coating process), but also can be used for spin-coating method, dip coating method.And when being used for the pattern formation method of slit coating method and drying under reduced pressure combination, effect of the present invention will obtain stronger performance.When photo-corrosion-resisting agent composition being coated on substrate by this slit coating method, usually photo-corrosion-resisting agent composition is stored in the supply container, be coated on the substrate through the mouth of disputing of pipeline and applying device etc. from here.Photosensitive polymer combination of the present invention, by this slit coating method, can apply out does not at high speed have film to come off and applies the good of spot to film.
Adopt the substrate of photosensitive polymer combination of the present invention by slit coating method formation photoresist film, afterwards can be according to handling with in the past identical method.Usually, under decompression or vacuum condition, remove at least a portion solvent, desolvate by curing to remove as required again, carry out image exposure by required pattern, and develop, by heating photoresist film is solidified again.In addition, in removing the operation of desolvating, not necessarily solvent all to be removed from film, as long as remove the degree that in follow-up operation, can not produce obstruction.These processing can at random be selected according to the purposes of the resist pattern of making, the kind of photosensitive polymer combination etc.
The photoresist pattern of Zhi Zaoing can be used for the manufacturing of various electronic products by this method.In photoresist film, because the homogeneity particular importance of face, pattern formation method of the present invention is used for the electronic product of function admirable such as the manufacturing of semiconductor element is very favourable.And, can adopt particularly preferably in need on larger substrate, forming in the manufacturing of the field of photoresist film such as LCD by slit coating etc.
The present invention is illustrated as follows.
Embodiment 1
's 8000 phenolics with respect to 100 weight portion weight-average molecular weight with polystyrene conversion, add 25 weight portions 2,3,4,4 '-tetrahydroxybenzophenone and 1, the carboxylate of 2-naphthoquinones two nitrine-5-sulfonic acid chloride is as emulsion, add 1000ppm fluorine class surfactant メ ガ Off ア Star Network R-08 (nonionic surfactant that Dainippon Ink. ﹠ Chemicals Inc produces) with respect to all solids composition, add propylene glycol methyl ether acetate and ethylene glycol n-butyl ether acetic acid ester again (at 1 atmospheric pressure, vapor pressure under 20 ℃ of conditions is 20Pa) mixed solvent (the mixed weight ratio is 70: 30), filter with 0.2 μ m after stirring filters, and makes photosensitive composite of the present invention.
Embodiment 2
Except solvent replacing that will dissolving is the mixed solvent (the mixed weight ratio is 60: 40) of propylene glycol methyl ether acetate and propylene-glycol diacetate (is 60Pa in the vapor pressure under 1 atmospheric pressure, the 20 ℃ of conditions), carry out similarly to Example 1, obtain the photosensitive composite of embodiment 2.
Embodiment 3
Except solvent replacing that will dissolving is the mixed solvent (the mixed weight ratio is 40: 60) of propylene glycol methyl ether acetate and 3-ethoxyl ethyl propionate (is 93Pa in the vapor pressure under 1 atmospheric pressure, the 20 ℃ of conditions), carry out similarly to Example 1, obtain the photosensitive composite of embodiment 3.
Embodiment 4
Except solvent replacing that will dissolving is the mixed solvent (the mixed weight ratio is 90: 10) of propylene glycol methyl ether acetate and benzylalcohol (is 13Pa in the vapor pressure under 1 atmospheric pressure, the 20 ℃ of conditions), carry out similarly to Example 1, obtain the photosensitive composite of embodiment 4.
Embodiment 5
Except solvent replacing that will dissolving is the mixed solvent (the mixed weight ratio is 95: 5) of propylene glycol methyl ether acetate and benzylalcohol (is 13Pa in the vapor pressure under 1 atmospheric pressure, the 20 ℃ of conditions), carry out similarly to Example 1, obtain the photosensitive composite of embodiment 5.
Embodiment 6
Except solvent replacing that will dissolving is the mixed solvent (the mixed weight ratio is 80: 15: 5) of propylene glycol methyl ether acetate and ethylene glycol n-butyl ether acetic acid ester (is 20Pa in the vapor pressure under 1 atmospheric pressure, the 20 ℃ of conditions) and benzylalcohol (is 13Pa in the vapor pressure under 1 atmospheric pressure, the 20 ℃ of conditions), carry out similarly to Example 1, obtain the photosensitive composite of embodiment 6.
Comparative example 1
Except the solvent replacing one-tenth with dissolving only is propylene glycol methyl ether acetate, carry out similarly to Example 1, obtain the photosensitive composite of comparative example 1.
Comparative example 2
Except solvent replacing that will dissolving is the mixed solvent (the mixed weight ratio is 40: 60) of propylene glycol methyl ether acetate and ro-butyl acetate (is 1000Pa in the vapor pressure under 1 atmospheric pressure, the 20 ℃ of conditions), carry out similarly to Example 1, obtain the photosensitive composite of comparative example 2.
Comparative example 3
Except solvent replacing that will dissolving is the mixed solvent (the mixed weight ratio is 40: 60) of propylene glycol methyl ether acetate and ethyl lactate (is 279Pa in the vapor pressure under 1 atmospheric pressure, the 20 ℃ of conditions), carry out similarly to Example 1, obtain the photosensitive composite of comparative example 2.
Comparative example 4
Except solvent replacing that will dissolving is the mixed solvent (the mixed weight ratio is 60: 40) of propylene glycol methyl ether acetate and ethyl cellosolve acetate (is 160Pa in the vapor pressure under 1 atmospheric pressure, the 20 ℃ of conditions), carry out similarly to Example 1, obtain the photosensitive composite of comparative example 4.
Comparative example 5
Except solvent replacing that will dissolving is the mixed solvent (the mixed weight ratio is 40: 60) of propylene glycol methyl ether acetate and ethyl cellosolve acetate (is 160Pa in the vapor pressure under 1 atmospheric pressure, the 20 ℃ of conditions), carry out similarly to Example 1, obtain the photosensitive composite of comparative example 5.
The evaluation of coating spot and coating homogeneity
Adopting the glass substrate of the band Cr of 120mm * 200mm, is to carry out slit coating under the state of 0.05mm from the distance of band Cr glass substrate at small-sized gap nozzle (wide 100mm).Coating speed is set at per second 100mm, inserts after the coating and carries out vacuum drying in 40 seconds in the vacuum drying oven.Vacuum pressure after 40 seconds at room temperature is adjusted to about 80Pa.Afterwards under 100 ℃ after curing for 90 seconds on the heating plate, obtain the resist film of 2.0 μ m.The gained resist film observed under the Na lamp have or not scale spot and striped spot, the coating spot is estimated.The coating homogeneity adopts Na ノ ス ペ Star Network M6500 type interference of light thickness analyzer (production of Na ノ メ ト リ Network ス ジ ヤ パ Application Co., Ltd.) to measure thickness and estimates.It adopts third-class level to estimate, and shoddy goods are expressed as 1, and little poor products are expressed as 2, and good product are expressed as 3.
The evaluation of spot during vacuum drying
After similarly adopting gap nozzle coating with the evaluation of above-mentioned coating spot and coating homogeneity, installing and locating pin in vacuum drying oven is provided with band Cr glass substrate thereon and carries out drying.After the vacuum drying, under 100 ℃ on heating plate dry 90 seconds, under the Na lamp, estimate the register pin vestige power in the vacuum drying oven.Adopt third-class level to estimate, the register pin vestige significantly is expressed as 1, and the register pin vestige is confirmed as and very trickle is expressed as 2, and what do not identify the register pin vestige is expressed as 3.
The mensuration of pattern form
After dripping on a small quantity on 4 inches the silicon chip, rotated for 2 seconds with 800 commentaries on classics, obtain pseudo-slit film.Then, insert and carry out vacuum drying in 40 seconds in the vacuum drying oven.Vacuum pressure after 40 seconds at room temperature is adjusted to about 80Pa.Then under 100 ℃ after curing for 90 seconds on the heating plate, obtain the resist film of 2.0 μ m.This resist film is exposed in the g+h line ledex (FX-604F) that ニ コ Application is made, in the tetramethyl ammonium hydroxide aqueous solution of 2.38 weight %, developed for 60 seconds down in 23 ℃.With the ratio of the exposure portion of 4.0 μ m mask size, unexposed portion is that 1: 1 exposure position is observed under SEM.Fig. 1 is its schematic cross-section.Adopt third-class level to estimate according to its shape, be similar to the situation of Fig. 1 (a) of back taper, be expressed as 1, shape is good slightly, is similar to the situation of Fig. 1 (b), is expressed as 2, is shaped as the good shape of taper, is similar to the situation of Fig. 1 (c), is expressed as 3.
The gained result is as shown in table 1.
Table 1
Table 1A: the evaluation result of screening characteristics and pattern form
Figure A20078003942100171
Table 1B: the vapor pressure of solvent
Figure A20078003942100172

Claims (7)

1, a kind of pattern formation method is characterized in that comprising:
Photosensitive polymer combination is coated on by the slit coating method its formation is filmed, above-mentioned photosensitive polymer combination contains alkali soluble resin, emulsion and mixed solvent, and above-mentioned mixed solvent contains propylene glycol methyl ether acetate and is cosolvent below the 150Pa in 1 atmospheric pressure, 20 ℃ of following vapor pressures;
Formed filming carried out drying under reduced pressure;
Proceed heat drying, remove at least a portion solvent with evaporation;
Carry out image exposure by required pattern;
Develop and make it form pattern;
Pattern after developing heated make its curing.
2, the described pattern of claim 1 formation method, wherein above-mentioned cosolvent is for being selected from benzylalcohol, the ethylene glycol butyl ether acetic acid esters, propylene glycol, propylene-glycol diacetate, propylene-glycol monoalky lether (carbon number of alkyl is 4～5), dipropylene glycol dialkyl ether (carbon number of alkyl is 1～5), dipropylene glycol monoalky lether (carbon number of alkyl is 1～5), diglycol dialkyl ether (carbon number of alkyl is 2～5), diglycol monotertiary alkyl ether (carbon number of alkyl is 1～5), the 3-ethoxyl ethyl propionate, 3-methoxyl-3-methyl butyl acetic acid esters, 3-methoxyl-3-methyl butanol, cosolvent in the group that butyl lactate and their potpourri constitute.
3, claim 1 or 2 described pattern formation methods, the content of above-mentioned cosolvent wherein is 5～70 weight % based on the weight of whole mixed solvents.
4, each described pattern formation method of claim 1～3, it further contains surfactant.
5, each described pattern formation method of claim 1～4, the pattern of its manufacturing is used for the manufacturing of LCD.
6, a kind of slit coating photosensitive polymer combination, it is characterized in that containing alkali soluble resin, emulsion and mixed solvent, above-mentioned mixed solvent contains propylene glycol methyl ether acetate and is cosolvent below the 150Pa in 1 atmospheric pressure, 20 ℃ of following vapor pressures.
7, the described photosensitive polymer combination of claim 6, it carries out drying under reduced pressure after coating.
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