CN107145037A - A kind of photoetching compositions and preparation method - Google Patents
A kind of photoetching compositions and preparation method Download PDFInfo
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- CN107145037A CN107145037A CN201710552426.1A CN201710552426A CN107145037A CN 107145037 A CN107145037 A CN 107145037A CN 201710552426 A CN201710552426 A CN 201710552426A CN 107145037 A CN107145037 A CN 107145037A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
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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
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
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Abstract
The present invention relates to technical field of macromolecules, more particularly to a kind of photoetching compositions and preparation method.Included according to the photoetching compositions of the present invention：The resin of 30 45 parts by weight, the background dye of 0.02 0.2 parts by weight, the organic solvent of 55 70 parts by weight；The resin includes photosensitive resin and film-forming resin, and the photosensitive resin includes diazo naphthoquinone resin and diphenylamine diazoresin.
Description
Technical field
The present invention relates to technical field of macromolecules, more particularly to a kind of photoetching compositions and preparation method.
Background technology
Photoresist is the key function material of progress photoetching process in large scale integrated circuit industry.Photoresist is through ultraviolet light
After irradiation, occurs series of chemical so that rate of dissolution of the photoresist in developer solution produces change before and after exposure, then passes through
Crossing the processes such as development, post bake, etching and striping just can be by specific high-precision pattern transfer to substrate surface to be processed.
In conventional method, SiNx typically is used as TFT passivation layer, because its dielectric constant k is high, the low original of transparency
Cause, holding resistance sluggish (RC delay) turns into the bottleneck of high aperture；It is now many to replace or match somebody with somebody using the material of low-k
SiNx is closed as passivation layer, at present using it is more be diazo naphthoquinone resinous materials.
However, there is presently no the resin material that can carry out double exposing so as to realize the figure preparation that more becomes more meticulous or tree
Oil/fat composition.
The content of the invention
It is an object of the invention to provide a kind of photoetching compositions that can be double exposed and preparation method, specific skill
Art scheme is as follows.
According to an aspect of the present invention there is provided a kind of photoetching compositions, including：The resin of 30-45 parts by weight,
The background dye of 0.02-0.2 parts by weight, the organic solvent of 55-70 parts by weight；The resin includes photosensitive resin and film forming tree
Fat, the photosensitive resin includes diazo naphthoquinone resin and diphenylamine diazoresin.
Different according to the photoactive spectrum of two kinds of photosensitive resins of the present invention, the primary photosensitive wavelength of diazo naphthoquinone resin is
365nm (i lines), the primary photosensitive wavelength of diphenylamine diazoresin is 420nm (g lines)；Therefore, it is possible to realize double exposure.
According to an embodiment of the invention, the mass ratio of the film-forming resin and photosensitive resin is (4-6)：1.
According to an embodiment of the invention, the mass ratio of the diphenylamine diazoresin and diazo naphthoquinone resin is
(2-4)：1.
According to an embodiment of the invention, the film-forming resin is water insoluble polymer, selected from epoxy resin,
The combination of any one or more in polyvinyl acetal resin and polyurethane resin.
According to an embodiment of the invention, described organic solvent be selected from glycol monoethyl ether, ethylene glycol monoethyl ether,
It is any one in dihydroxypropane single-ether, MEK, butyl acetate, dioxane, 1-METHYLPYRROLIDONE, methanol and tetrahydrofuran
Plant or a variety of combinations.
According to an embodiment of the invention, the background dye is pure selected from alkaline bright blue, crystal violet, Victoria
The combination of any one or more in blue, indigo, crystal violet, malachite green and solvent blue.
According to an embodiment of the invention, the diphenylamine diazoresin has following structure：
Wherein, n is selected from 2-1000 integer；W is methylene, and X is selected from hydrogen, methoxyl group or methyl, and Y is nitro, and Z is selected from first
Base or ethyl, R-Selected from hexafluoro-phosphate radical, DBSA root, dodecyl sodium sulfonate root, p-methyl benzenesulfonic acid root, equal front three
Benzene sulfonic acid root or naphthalenesulfonate anion.
According to an embodiment of the invention, wherein, n is 6, R-For sym-toluenesulfonic acid root anion, X is H, and Z is
Methyl.
According to an embodiment of the invention, the diazo naphthoquinone resin has following structure：
According to another aspect of the present invention, additionally provide according to a kind of preparation side of photoetching compositions of the present invention
Method, comprises the following steps：Background dye is dissolved in organic solvent, film-forming resin, diazo naphthoquinone resin and hexichol is then added
Amine diazo resin, dissolution filter obtains the photoetching compositions.
Beneficial effects of the present invention are：The photoetching compositions of double exposure can be realized the invention provides a kind of, can
Double exposed using dual masks plate (Mask), to realize that superfinishing refines the preparation of figure.
Brief description of the drawings
Fig. 1 is the photoactive spectrum figure of diazo naphthoquinone resin.
Fig. 2 is the photoactive spectrum figure of diphenylamine diazoresin.Wherein, numeral 1 to 7 represents that through wavelength be 420nm's successively
Absorbance after ultraviolet light (g lines) irradiation 0s, 10s, 20s, 30s, 40s, 50s, 60s.
Fig. 3 is the molecular weight distribution test result of the diphenylamine diazoresin of the present invention.
Fig. 4 is diphenylamine diazoresin of the invention and film-forming resin, the crosslinking schematic diagram of passivation layer.
Fig. 5 is the schematic diagram double exposed using dual masks plate；Wherein, the mask plates of A- first, the mask plates of B- second,
Films of the PR III- containing photoresist, PR I- the first photoresist film figures, PR II- the second photoresist film figures.
Embodiment
Embodiment is only the description of the invention, without constituting the limitation to present invention, below in conjunction with
Specific embodiment is further described and described to the present invention.
The photoetching compositions of double exposure can be realized it is an object of the invention to provide a kind of, dual masks plate can be used
(Mask) double exposed, to realize that superfinishing refines the preparation of figure.
According to an aspect of the present invention there is provided a kind of photoetching compositions, including：The resin of 30-45 parts by weight,
The background dye of 0.02-0.2 parts by weight, the organic solvent of 55-70 parts by weight；The resin includes photosensitive resin and film forming tree
Fat, the photosensitive resin includes diazo naphthoquinone resin and diphenylamine diazoresin.
Different according to the photoactive spectrum of two kinds of photosensitive resins of the present invention, the primary photosensitive wavelength of diazo naphthoquinone resin is
365nm (i lines), the primary photosensitive wavelength of two diazo resins is 420nm (g lines)；Therefore, it is possible to realize double exposure.
According to an embodiment of the invention, the mass ratio of the film-forming resin and photosensitive resin is (4-6)：1.Example
Such as, the mass ratio of film-forming resin and photosensitive resin can be 4:1、4.2:1、4.5:1、5:1、5.5:1、6:1 etc..
According to an embodiment of the invention, the mass ratio of the diphenylamine diazoresin and diazo naphthoquinone resin is
(2-4)：1.For example, the mass ratio of diphenylamine diazoresin and diazo naphthoquinone resin can be 2:1、2.2:1、2.5:1、3:1、
3.5:1、3.8:1、4:1 etc..
According to an embodiment of the invention, the film-forming resin is water insoluble polymer, selected from epoxy resin,
The combination of any one or more in polyvinyl acetal resin and polyurethane resin.
According to an embodiment of the invention, described organic solvent be selected from glycol monoethyl ether, ethylene glycol monoethyl ether,
It is any one in dihydroxypropane single-ether, MEK, butyl acetate, dioxane, 1-METHYLPYRROLIDONE, methanol and tetrahydrofuran
Plant or a variety of combinations.
According to an embodiment of the invention, the background dye is pure selected from alkaline bright blue, crystal violet, Victoria
The combination of any one or more in blue, indigo, crystal violet, malachite green and solvent blue.
According to an embodiment of the invention, the diphenylamine diazoresin has following structure：
Wherein, n is selected from 2-1000 integer；Preferably be selected from 2-100, further preferably from 2-10, be selected from 2,4,6,8 or
10, W be methylene, and X is selected from hydrogen, methoxyl group or methyl, and Y is nitro, and Z is selected from methyl or ethyl, R-Selected from hexafluoro-phosphate radical, ten
Dialkyl benzene sulfonic acids root, dodecyl sodium sulfonate root, p-methyl benzenesulfonic acid root, sym-toluenesulfonic acid root or naphthalenesulfonate anion.
According to an embodiment of the invention, wherein, n is 6, R-For sym-toluenesulfonic acid root anion, X is H, and Z is
Methyl.
The preparation method of diphenylamine diazoresin
The synthetic route of N- ethyl 2- nitrodiphenylamine 4- diazols is as follows：
1) 300g (1.49mol) DNFB is added in 1485mL absolute ethyl alcohols, dissolves by heating, add
173g (1.63mol) anhydrous Na2CO3.It is heated to reflux, instills 196.9g (1.63mol) N-ethylaniline, drips off reaction 6h, cooling
12h is placed, compound A is obtained, is peony prismatic monocrystal, yield 299g, yield 70%.
2) 180g (0.63mol) compounds A is dissolved in the ethanol of 1000mL 95%, adds 66.5g (0.63mol) anhydrous
Na2CO3, it is heated to reflux, 301g (1.25mol) Na is slowly added dropwise2S·9H2O is dissolved in the solution of 500mL water, and about 2h is dripped off, then
Flow back 4h, cooling.Reaction mixture is poured into 2000mL water, a period of time is stood, layering is poured out the water on upper strata, added
A small amount of water washing, obtains brown oil aniline B, and aniline is easily oxidized unstable, it is necessary to be translated into sulfuric acid in atmosphere
Salt form.
1000mL 10%H are added in aniline B2SO465 DEG C of dissolving grease are heated to, are filtered while hot, crystallisation by cooling uses this
Saturated solution repeated recrystallize residue grease, until being separated out without crystal, obtains compound B sulfate, is golden flake crystalline
Body, yield 249g, yield 69%.
3) 100g (0.28mol) compounds B sulfate is added to 360mL 5%H2SO4In, add 600g trash ices, ice
NaNO is slowly added dropwise under 0-5 DEG C of water-bath keeping temperature, stirring2Solution (NaNO2Solution is by 23g (0.33mol) NaNO2It is dissolved in
110mL water is obtained), completion of dropping continues to stir 2h, obtains diazol C.
Filter and 151g ZnCl are added in reacted mixed liquor, filtrate2Saturated solution, there are a large amount of yellow solids to separate out,
Suction filtration, ethanol is washed 2 times, is air-dried in fume hood, is obtained diazol C 1/2ZnCl2Double salt D, yield 72.9g, yield 60%.
IR(cm-1):ν=2981.4cm-1(w,H2C-H),2224.0cm-1(s,C-N2 +),1601cm-1,1581cm-1,
1537cm-1(vs,Ar)；
1H NMR(400MHz,D2O,δ):8.67(d,1H,H Ar-NO2),8.19(t,1H,H Ar-N2 +),7.54,7.30,
7.23,7.14(m,6H,H Ar),4.05(q,2H,CH2),1.12(t,3H,CH3)。
Anal.calcd for C14H13N4O2 +·HSO4 -(%):C 45.90,H 3.85,N 15.39；Found (%):C
44.42,H 3.46,N 14.73。
By above-mentioned diazol C 1/2ZnCl2Double salt D is condensed with paraformaldehyde, diazo resin is made, polymerization is：Weight
Nitrogen salt C 1/2ZnCl2Double salt D (0.039mol) is added portionwise in the sulfuric acid of 52mL 98% under agitation, after being completely dissolved,
Finely ground paraformaldehyde (1.4g, 0.047mol) is added portionwise at 0-5 DEG C, this temperature of holding 5h is added.Reaction mixture is delayed
Slowly pour into the frappe ethanol of 230mL, and stir, after enough water dissolvings, add enough ZnCl2Saturated solution,
There are a large amount of solids to separate out, suction filtration, ethanol is washed 2 times, air-dried in fume hood, obtain corresponding water-soluble formaldehyde contracting diazo resin E.
Above-mentioned water-soluble formaldehyde contracting diazo resin (0.04mol) is dissolved in 200mL, filters out impurity.Under agitation, filtrate
The middle saturated aqueous solution that (9.99g, 0.045mol) sym-toluenesulfonic acid sodium is added dropwise, anion takes place when pH is 2.5 and hands over
Change, add 10% NaCO3Solution adjusts pH to 7, and the precipitation that suction filtration is obtained is washed with water 3 times, 27 DEG C are dried in vacuum overnight, and obtain
To formaldehyde contracting N- ethyl -2- nitrodiphenylamine 4- diazonium sym-toluenesulfonic acid resin F (yield 77%).
PARA FORMALDEHYDE PRILLS(91,95) contracting N- ethyl -2- nitrodiphenylamine 4- diazonium sym-toluenesulfonic acid resins are identified that its data is as follows：
IR(cm-1):ν=2971.8cm-1(w,H2C-H),2200.0cm-1(s,C-N2 +),1588.2cm-1,1543.4cm-1
(vs,Ar)；
1H NMR(400MHz,D2O,δ):8.67(d,1H,H-Ar-NO2),8.19(t,1H,H-Ar-N2 +),7.54,7.30,
7.23,7.14(m,6H,H-Ar),4.05(q,2H,CH2),1.12(t,3H,CH3)。
Gel chromatography determines the distribution of molecular resin amount, and the result for carrying software calculating by system is as shown in Figure 3.
Similarly, other different substituents can be prepared by similar synthetic method by using corresponding raw material
Diphenylamine diazoresin.
According to an embodiment of the invention, the diazo naphthoquinone resin has following structure：
The diazo naphthoquinone resin can be commercially available, example
Such as by the BP207 of Hubei Gu Run Science and Technology Co., Ltd. sale, BP208, BP209, BP210, BP211, BP212,702 just
Glue, 703 positive photoresists etc..The main component of these products is organic compound, the cresol of the adjacent diazo naphthoquinone base of photonasty group
The mixture of urea formaldehyde and solvent.
According to another aspect of the present invention, additionally provide according to a kind of preparation side of photoetching compositions of the present invention
Method, comprises the following steps：Background dye is dissolved in organic solvent, film-forming resin, diazo naphthoquinone resin and hexichol is then added
Amine diazo resin, dissolution filter obtains the photoetching compositions.Filtering can be carried out using such as filter paper.
The addition sequence of film-forming resin, diazo naphthoquinone resin and diphenylamine diazoresin three be it is arbitrary, for example can be with
These three resins are added simultaneously, film-forming resin, diazo naphthoquinone resin, diphenylamine diazoresin can be sequentially added, sequentially added
Film-forming resin, diphenylamine diazoresin, diazo naphthoquinone resin, sequentially add diazo naphthoquinone resin, film-forming resin, diphenylamine diazonium
Resin, sequentially adds diazo naphthoquinone resin, diphenylamine diazoresin, film-forming resin, sequentially adds diphenylamine diazoresin, diazonium
Naphthoquinones resin, film-forming resin, sequentially add diphenylamine diazoresin, film-forming resin, diazo naphthoquinone resin etc..
Photoetching compositions and preparation method
Embodiment 1
Photoetching compositions, including：The parts by weight of alkaline bright blue 0.02, the parts by weight of epoxy resin 30, diazo naphthoquinone resin
(wherein, n=2, W are CH for the parts by weight of BP207 1.5, diphenylamine diazoresin2、R-It is first for dodecyl sodium sulfonate root anion, X
Epoxide, Y are that nitro, Z are methyl) 5.5 parts by weight, the parts by weight of glycol monoethyl ether 62.8.
The preparation method of photoetching compositions：0.02g alkaline bright blues are dissolved in 62.8g glycol monoethyl ethers, then successively
1.5 parts by weight diazo naphthoquinone resins, 5.5g diphenylamine diazoresins, 30g epoxy resin are added, dissolves and is filtered with filter paper, obtained
To the photoetching compositions of embodiment 1.
Embodiment 2
Photoetching compositions, including：The parts by weight of crystal violet 2, the parts by weight of polyurethane resin 25, diazo naphthoquinone resin B P210
(wherein, n=6, W are CH for 1 parts by weight, diphenylamine diazoresin2、R-It is that hydrogen, Y are nitre for sym-toluenesulfonic acid root anion, X
Base, Z be methyl) 4 parts by weight, the parts by weight of dihydroxypropane single-ether 68.
The preparation method of photoetching compositions：2g crystal violets are dissolved in 68g dihydroxypropane single-ethers, 4g bis- is then sequentially added
Aniline diazo resin, 1g diazo naphthoquinones resin, 25g polyurethane resins, dissolve and are filtered with filter paper, obtain the photoetching of embodiment 2
Glue composition.
Embodiment 3
Photoetching compositions, including：The parts by weight of Victoria pure blue 0.2, the parts by weight of polyvinyl acetal resin 27, diazonium
(wherein, n=1000, W are CH for the parts by weight of naphthoquinones resin B P209 1.2, diphenylamine diazoresin2、R-For hexafluoro-phosphate radical it is cloudy from
Son, X are that methyl, Y are that nitro, Z are ethyl) 3.6 parts by weight, the parts by weight of dioxane 68.
The preparation method of photoetching compositions：0.2g Victoria pure blues are dissolved in 68g dioxane, then sequentially added
1.2g diazo naphthoquinones resin, 27g polyvinyl acetal resins, 3.6g diphenylamine diazoresins, dissolve and are filtered with filter paper, obtained
The photoetching compositions of embodiment 3.
Embodiment 4
Photoetching compositions, including：The parts by weight of solvent blue 1, the parts by weight of polyurethane resin 33, diazo naphthoquinone resin B P211
(wherein, n=10, W are CH for 2 parts by weight, diphenylamine diazoresin2、R-It is that methyl, Y are nitro, Z for naphthalenesulfonate anion, X
For methyl) 6 parts by weight, the parts by weight of methanol 58.
The preparation method of photoetching compositions：1g solvent blues are dissolved in 58g methanol, 6g diphenylamine diazoniums are then sequentially added
Resin, 33g polyurethane resins, 2g diazo naphthoquinone resins, dissolve and are filtered with filter paper, obtain the photoetching compositions of embodiment 4.
Embodiment 5
Photoetching compositions, including：The parts by weight of crystal violet 0.5, the parts by weight of polyvinyl acetal resin 36, diazo naphthoquinone tree
(wherein, n=8, W are CH for the parts by weight of fat BP212 3, diphenylamine diazoresin2、R-It is hydrogen, Y for p-methyl benzenesulfonic acid root anion, X
Be ethyl for nitro, Z) 6 parts by weight, the parts by weight of tetrahydrofuran 54.5.
The preparation method of photoetching compositions：0.5g crystal violets are dissolved in 54.5g tetrahydrofurans, 36g is then sequentially added
Polyvinyl acetal resin, 3g diazo naphthoquinones resin, 6g diphenylamine diazoresins, dissolve and are filtered with filter paper, obtain embodiment 5
Photoetching compositions.
Embodiment 6
Photoetching compositions, including：Indigo 1.5 parts by weight, the parts by weight of epoxy resin 32, diazo naphthoquinone resin B P208
(wherein, n=100, W are CH for 2.5 parts by weight, diphenylamine diazoresin2、R-It is first for DBSA root anion, X
Base, Y are that nitro, Z are ethyl) 5 parts by weight, the parts by weight of MEK 59.
The preparation method of photoetching compositions：59g MEKs are dissolved in by 1.5g is indigo, then sequentially add 32g asphalt mixtures modified by epoxy resin
Fat, 5g diphenylamine diazoresins, 2.5g diazo naphthoquinone resins, dissolve and are filtered with filter paper, obtain the photoresist combination of embodiment 6
Thing.
Embodiment 7
Photoetching compositions, including：The parts by weight of malachite green 1.7, the parts by weight of polyvinyl acetal resin 28, diazo naphthoquinone
(wherein, n=500, W are CH for the parts by weight of 703 positive photoresist of resin 1.8, diphenylamine diazoresin2、R-For sym-toluenesulfonic acid root it is cloudy from
Son, X are that methoxyl group, Y are that nitro, Z are methyl) 4.5 parts by weight, the parts by weight of 1-METHYLPYRROLIDONE 64.
The preparation method of photoetching compositions：1.7g malachite greens are dissolved in 64g 1-METHYLPYRROLIDONEs, then successively
1.8g diazo naphthoquinones resin, 4.5g diphenylamine diazoresins, 28g polyvinyl acetal resins are added, dissolves and is filtered with filter paper,
Obtain the photoetching compositions of embodiment 7.
Double exposure
It can be carried out according to the double exposure of the present invention by following steps, wherein diazo naphthoquinone resin is used as positivity light
Photoresist, diphenylamine diazoresin is used as negative photoresist.Fig. 1 is the photoactive spectrum figure of diazo naphthoquinone resin.Fig. 2 is diphenylamines weight
The photoactive spectrum figure of nitrogen resin.As seen from Figure 1, the primary photosensitive wavelength of diazo naphthoquinone resin is near 365nm.By Fig. 2
As can be seen that the primary photosensitive wavelength of diphenylamine diazoresin is near 420nm, in addition, with the extension of time for exposure, extinction
Angle value constantly reduces, i.e. the content of diphenylamine diazoresin is constantly reduced, and under 420nm wavelength irradiate 60s after diphenylamines weight
Nitrogen resin is decomposed completely.
(1) expose for the first time
The photoetching compositions of the present invention are applied to plasma enhanced chemical gas with 2000-6000 turns/min rotating speed
Mutually deposition has SiO2(thickness is) glass substrate on, 100 DEG C of front bakings form the film PR containing photoresist in 2-10 minutes
III, then carries out first time exposure with exposure machine, and wavelength is 365nm (i lines), and exposure intensity is 30-180mJ/cm2。
Because the primary photosensitive wavelength of diazo naphthoquinone resin is near 365nm (i lines) (as shown in Figure 1), therefore in 365nm
Ultraviolet light when occur light decompose.With developing liquid developing 20 seconds, photosensitive to be partially soluble in developer solution and remove, not photosensitive part
Develop to picture.Simultaneously as the primary photosensitive wavelength of diphenylamine diazoresin is 420nm (g lines) (as shown in Figure 2), therefore
Do not reacted during 365nm ultraviolet light, photosensitive part and not photosensitive part are left insoluble in developer solution.Therefore
Obtain and first mask plate A images identical the first photoresist film figure PR I.
(2) second of exposure
Second is carried out using wavelength to photoetching compositions for 420nm ultraviolet light (g lines) to expose, exposure intensity is
30-180mJ/cm2。
Because the primary photosensitive wavelength of diphenylamine diazoresin is near 420nm (g lines), therefore the hexichol when exposing for second
Amine diazo resin is crosslinked with film-forming resin.With developing liquid developing 20 seconds, photosensitive part developed to picture, not photosensitive to be partially soluble in
Developer solution and remove.Simultaneously as the primary photosensitive wavelength of diazo naphthoquinone resin is 365nm (i lines), therefore in 420nm purple
Do not occur light decomposition during outer light irradiation, photosensitive part and not photosensitive part are left insoluble in developer solution.So as to obtain the
Two photoresist film figure PRII.
The pattern double exposed by dual masks plate, it is possible to achieve the system of the wide figure of more fine rule under the limitation of mask plate line width
It is standby.As in Fig. 5, the first mask plate A, the second mask plate B preparation minimum feature or line-spacing are 1 μm, by by two mask plates
0.5 μm of dislocation, (i.e. the first photoresist film figure I line width is 1 μm, and the second photoetching for the exposure of achievable 0.5 μm of line width figure
Glued membrane figure II line width is 0.5 μm).
Fig. 4 is diphenylamine diazoresin of the invention and film-forming resin, the crosslinking schematic diagram of passivation layer.In exposure, by
In nitro electron attraction, cause benzene diazonium mainly to occur heterolytic fission, produce substantial amounts of hexichol amine cation, and on film-forming resin
- OH nucleopilic reagents react.In addition, hexichol amine cation can also be with SiO2Film surface and the hydrogen bond of hydrone formation are handed over
Connection, result is the photoresist and SiO of exposed portion2Surface is bonded together by hydrogen bond, will not be occurred in developing process de-
From, and the photoresist of unexposed portion does not have this adhesive effect, is removed after development.
In the present invention, development twice uses identical developer solution, and the developer solution is by 1-5 mass parts
Na2SiO3, the phenmethylol of 8-10 mass parts, the lauryl sodium sulfate of 4-8 mass parts be dissolved in the water of 80-120 mass parts and make
Standby.
Obviously, those skilled in the art can carry out the essence of various changes and modification without departing from the present invention to the present invention
God and scope.So, if these modifications and variations of the present invention belong to the scope of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to comprising including these changes and modification.
Claims (10)
1. a kind of photoetching compositions, it is characterised in that including：The resin of 30-45 parts by weight, the background of 0.02-0.2 parts by weight
The organic solvent of dyestuff, 55-70 parts by weight；The resin includes photosensitive resin and film-forming resin, and the photosensitive resin includes weight
Quinoline quinone resin and diphenylamine diazoresin.
2. a kind of photoetching compositions according to claim 1, it is characterised in that the film-forming resin and photosensitive resin
Mass ratio is (4-6)：1.
3. a kind of photoetching compositions according to claim 1, it is characterised in that the diphenylamine diazoresin and diazonium
The mass ratio of naphthoquinones resin is (2-4)：1.
4. a kind of photoetching compositions according to claim 1, it is characterised in that the film-forming resin is selected from asphalt mixtures modified by epoxy resin
The combination of any one or more in fat, polyvinyl acetal resin and polyurethane resin.
5. a kind of photoetching compositions according to claim 1, it is characterised in that the organic solvent is selected from ethylene glycol list
Methyl ether, ethylene glycol monoethyl ether, dihydroxypropane single-ether, MEK, butyl acetate, dioxane, 1-METHYLPYRROLIDONE, methanol and
The combination of any one or more in tetrahydrofuran.
6. a kind of photoetching compositions according to claim 1, it is characterised in that it is gorgeous that the background dye is selected from alkalescence
The combination of any one or more in indigo plant, crystal violet, Victoria pure blue, indigo, crystal violet, malachite green and solvent blue.
7. a kind of photoetching compositions according to claim 1, it is characterised in that the diphenylamine diazoresin have with
Lower structure：
Wherein, n is selected from 2-1000 integer；W is methylene, and X is selected from hydrogen, methoxyl group or methyl, and Y is nitro, Z be selected from methyl or
Ethyl, R-Selected from hexafluoro-phosphate radical, DBSA root, dodecyl sodium sulfonate root, p-methyl benzenesulfonic acid root, mesitylene sulphur
Acid group or naphthalenesulfonate anion.
8. a kind of photoetching compositions according to claim 7, it is characterised in that wherein, n is 6, R-For mesitylene sulphur
Acid radical anion, X is H, and Z is methyl.
9. a kind of photoetching compositions according to claim 1, it is characterised in that the diazo naphthoquinone resin has following
Structure：
10. a kind of preparation method of photoetching compositions as described in any one of claim 1~9, it is characterised in that including with
Lower step：Background dye is dissolved in organic solvent, film-forming resin, diazo naphthoquinone resin and diphenylamine diazonium tree is then added
Fat, dissolution filter obtains the photoetching compositions.
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