CN107844028A - A kind of photoresist, preparation method and its photoetching process - Google Patents
A kind of photoresist, preparation method and its photoetching process Download PDFInfo
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- CN107844028A CN107844028A CN201711085268.XA CN201711085268A CN107844028A CN 107844028 A CN107844028 A CN 107844028A CN 201711085268 A CN201711085268 A CN 201711085268A CN 107844028 A CN107844028 A CN 107844028A
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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
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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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
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- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
The present invention relates to technical field of lithography, in particular to a kind of photoresist, preparation method and its photoetching process.The photoresist is mainly made up of macromolecule resin, small-molecular-weight resin, sensitising agent and solvent；The photoresist is mainly made up of following components by mass percentage：Macromolecule resin 15 25%, small-molecular-weight resin 2 16%, sensitising agent 3 15% and solvent 50 80%.The molecular weight of small-molecular-weight resin is relatively low, the chain structure of molecule is relatively short, it is relatively small to occupy volume, steric hindrance is relatively small, can be filled between the space of macromolecule resin formation, and pass through intermolecular force between small-molecular-weight resin and macromolecule resin, improve adhesion between the two, further increase the compact structure of photoresist after baking, improve adhesion, avoid floating glue.
Description
Technical field
The present invention relates to technical field of lithography, in particular to a kind of photoresist, preparation method and its photoetching process.
Background technology
Photoresist is also known as photoresist, the photaesthesia mixture being made up of photosensitive resin, sensitising agent and solvent etc., its
Under ultraviolet light beams irradiation, solidification or degradation reaction can be crosslinked.In integrated circuit, liquid crystal display, solar energy
The electronic applications such as volt, MEMS have a wide range of applications.Photoetching compositions are used for photoetching process manufacture microelectronic component, such as
Manufacture computer chip and integrated circuit etc..It is generally required by being coated on the backing material such as surface such as silicon chip, sapphire sheet
One layer of uniform photoresist, is then toasted with the solvent in evaporative removal glue, is then exposed, and makes the master in photoresist
Want composition to react under light illumination and change constituent structure and its dissolution velocity in developer solution, then pass through development realization and cover
Transfer of the film pattern on substrate, the litho pattern of needs is formed, post bake is dried after finally carrying out to improve photoresist in etching work
Heat resistance and elching resistant energy in skill.
Existing common positive photoresist is phenolic resin with Main System, its adhesion in substrate compared with negtive photoresist
Difference, glue rate height is floated after causing development, production yield is low, and rework rate is high.
There is the adhesion that some production technologies improve photoresist at present, as coated tackifier HMDS, substrate cleaning before spin coating
High temperature pretreatment etc. afterwards.But because HMDS toxicity is larger, be hazardous to the human body, so many producers avoid using as far as possible.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of photoresist have fine and close structure after the baking of described photoresist,
So as to improve adhesion, the situation of drift glue is greatly improved.
The second object of the present invention is to provide a kind of preparation method of described photoresist, the preparation method technique letter
List, stable operation are controllable, and have fine and close structure after the photoresist baking being prepared, and can effectively improve photoresist
Adhesion.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of photoresist, mainly it is made up of macromolecule resin, small-molecular-weight resin, sensitising agent and solvent；Preferably, institute
Photoresist is stated mainly to be made up of following components by mass percentage：
Macromolecule resin 15-25%, small-molecular-weight resin 2-16%, sensitising agent 3-15% and solvent 50-80%.
Preferably, the photoresist is mainly made up of following components by mass percentage：
Macromolecule resin 17-20%, small-molecular-weight resin 4-8%, sensitising agent 4-8% and solvent 64-70%.More
Preferably, the photoresist is mainly made up of following components by mass percentage：Macromolecule resin 17.01-
19.68%th, small-molecular-weight resin 4.68-7.29%, sensitising agent 5.4-7.05% and solvent 68.5-69%.
Photoresist of the present invention is by introducing small-molecular-weight resin, the compactness of structure after increase photoresist baking,
So as to improve adhesion, improve drift glue situation.
Preferably, the molecular weight ranges of the small-molecular-weight resin are 1000-3000, the molecule of the macromolecule resin
Measure as 7000-12000.
Because the molecular weight of macromolecule resin is of a relatively high, the chain structure of molecule is longer, and volume is occupied with wrapped configuration
Larger, steric hindrance is larger, and compactness is relatively poor, and the transmitance of vapor and oxygen is high, the main component as photoresist
Compact structure deficiency after baking, the poor adhesion in substrate, obvious drift glue after development be present；And small-molecular-weight resin
Molecular weight it is relatively low, the chain structure of molecule is relatively short, occupies that volume is relatively small, and steric hindrance is relatively small, can be with
It is filled between the space of macromolecule resin formation, and by intermolecular between small-molecular-weight resin and macromolecule resin
Active force, adhesion between the two is improved, further increases the compact structure of photoresist after baking, improve adhesion,
Avoid floating glue situation.
The molecular weight of small-molecular-weight resin within the above range, avoids molecular weight too small, and the free degree is excessive in the photoresist,
After baking is developed, easily it is lost in, reduces the anti-etching ability of photoresist；Also avoid molecular weight excessive, it is not easy to fully to fill out
Fill between the space of macromolecule resin, it is impossible to effectively improve the compactness of structure.
Preferably, the small-molecular-weight resin is including general structure Resin in one or more；Wherein, n1For 7-22 integer, n2For 8-25 integer, n3For
6-20 integer；R1、R2And R3For hydrogen or alkyl.
Phenyl ring and hydroxyl are contained in the construction unit of above-mentioned small-molecular-weight resin, phenyl ring provides one for small-molecular-weight resin
Fixed rigid structure, improve mechanical strength；Hydroxyl, can be with the active function groups in macromolecule resin as active function groups
Intermolecular hydrogen bonding effect is formed, also can improve small-molecular-weight resin and macromolecule tree as the site acted on substrate surface
The bond strength of fat, to the adhesiveness of substrate after increase baking.
Preferably, the macromolecule resin includes phenolic resin, has construction unitResin, have
Construction unitResin and there is construction unitResin in one or more.
It is furthermore preferred that the macromolecule resin is with construction unitResin, there is construction unitResin and there is construction unitResin in one or more.
When macromolecule resin has identical construction unit with small-molecular-weight resin, the compatibility of two kinds of resins is more preferable, small
Molecular weight resin, which can be fully compatible, to be filled between macromolecule resin, and the intermolecular hydrogen bonding between the hydroxyl in structure
Effect, can effectively improve improve two kinds of resins bond strength, improve baking after compact structure, so as to improve adhesiveness and
Etch-resistance energy.
Preferably, the mass percent that the small-molecular-weight resin accounts for macromolecule resin is 20-60%.It is furthermore preferred that
The mass percent that the small-molecular-weight resin accounts for macromolecule resin is 30-40%.
Small-molecular-weight resin is filled among the space of macromolecule resin, it is necessary to which appropriate dosage, just can guarantee that fully
Filling, improve adhesiveness；If the small-molecular-weight resin added is very few, filling is insufficient, compact structure deficiency, adhesiveness
Difference, anti-etching ability are low；If the small-molecular-weight resin added is excessive, there are residue, remaining small molecule in addition to space is filled
Amount resin floats on photoresist top layer, and drift glue is easily caused after development, or spacing is larger between causing macromolecule resin, adhesion
Property reduce.
Preferably, the sensitising agent includes diphenyl iodine hexafluorophosphoric acid ester, diphenyl iodine trifluoromethayl sulfonic acid ester, two
It is the fluorine n-butanesulfonic acid ester of phenyl-iodide nine, diphenyl iodine perfluoro-n-octane sulphonic acid ester, diphenyl iodine camphorsulfonic acid ester, double
(4- tert-butyl-phenyls) iodine camphorsulfonic acid ester, double (4- tert-butyl-phenyls) iodine trifluoromethayl sulfonic acid esters, double (trifluoromethyl sulphurs
Acyl group) diazomethane, 2,1,4- diazonium naphthoquinone sulphonates, 2,1,5- diazonium naphthoquinone sulphonates, 2,3,4- trihydroxybenzophenones,
One or more in the nitrine -4- sulfonic acid of 1,2- benzoquinones two and the nitrine -5- sulfonic acid of 1,2- naphthoquinones two.
Preferably, the solvent includes the solvent that can dissolve the macromolecule resin, small-molecular-weight resin and sensitising agent.
It is furthermore preferred that the solvent includes diethyl carbonate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, second
Sour N-butyl, isobutyl acetate, methyl cyclohexyl ester, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, second
Glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetate, propylene glycol phenyl
Ether acetate, ethylene acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, methyl lactate, ethyl lactate, lactic acid
N-butyl, N_amyl lactate, diethyl malonate, repefral, diethyl phthalate, N- methyl formyls
Amine, DMF, N, N- diethylformamides, acetamide, N- methylacetamides, DMA, N-
Methyl propanamide, 1-METHYLPYRROLIDONE, dimethyl disulfide, diethyl sulfide, thiophene, thiophane, dimethyl sulfoxide (DMSO), sulfolane,
It is 1,3- propane sultones, methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, pentane, isopentane, n-hexane, different
In hexane, normal heptane, benzene,toluene,xylene, acetone, methyl ethyl ketone, ethylene glycol, propane diols, ether and ethylene glycol ethyl ether
It is one or more.
Preferably, the photoresist also includes surfactant.It is furthermore preferred that the mass percent of the surfactant
For 1-1.5%.The surfactant includes DOW CORNING Z-6011, union carbide corporation of U.S. A-1100, Chinese Academy of Sciences KH-550.
Present invention also offers a kind of preparation method of the photoresist, comprise the following steps：
After each component mixed dissolution, photoresist is filtrated to get.Preferably, with 0.02 μm and the filter membrane mistake in following aperture
Filter.
Present invention also offers a kind of photoetching process of the photoresist, comprise the following steps：
The photoresist is applied to substrate surface, preliminary drying is dried, and development is soaked after ultraviolet photoetching, after then cleaning substrate
Dry post bake.
Preferably, the temperature that the preliminary drying is dried is 90-110 DEG C, and the time that the preliminary drying is dried is 60-150s.
Preferably, the ultraviolet light is g lines ultraviolet light or i line ultraviolet lights.
Preferably, the liquid of the immersion development is alkaline aqueous solution.It is furthermore preferred that the alkaline aqueous solution includes tetramethyl
The aqueous solution, potassium hydroxide aqueous solution, sodium hydrate aqueous solution or one kind or more in ammonium hydroxide aqueous solution of base ammonium hydroxide
Kind.It is furthermore preferred that the alkaline aqueous solution is the aqueous solution of 2.38wt% TMAH.
Preferably, the temperature for drying post bake is 115-125 DEG C, and the time for drying post bake is 90-180s.
Compared with prior art, beneficial effects of the present invention are：
(1) photoresist adhesion property of the invention is good, introduces small-molecular-weight resin, increase photoresist baking in the photoresist
The compactness of structure afterwards, adhesion is improved, improve drift glue situation；
(2) molecular weight of the small-molecular-weight resin in the present invention is relatively low, and the chain structure of molecule is relatively short, occupies body
Product is relatively small, and steric hindrance is relatively small, can be filled between the space of macromolecule resin formation, and small-molecular-weight
By intermolecular force between resin and macromolecule resin, adhesion between the two is improved, further increases photoresist
Etch-resistance energy after baking；
(3) preparation method of photoresist of the invention is simple, easily operated, and operating condition is gentle, and repeatability can be good；
(4) etching technics of the invention, using the good photoresist of adhesiveness, the glued membrane of unexposed reactive moieties is deposited in base
Basal surface forms photoengraving pattern, and the compact texture after photoresist drying plays a part of hindering etching, resistance to so as to improve photoresist
Etching performance.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described.
Fig. 1 is the development effect figure of the photoresist of the embodiment of the present invention；
Fig. 2 is sectional view after the development of the photoresist of the embodiment of the present invention；
Fig. 3 is the development effect figure of the photoresist of comparative example；
Fig. 4 is the etching section design sketch of the photoresist of the embodiment of the present invention；
Fig. 5 is the etching section design sketch of the photoresist of comparative example.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
The composition of the photoresist of the present embodiment is：
Macromolecule resin 19.68g, small-molecular-weight resin 4.92g, 2,1,4- diazonium naphthoquinone sulphonate 5.4g, U.S.'s connection
Carbon company A-1100 1.5g, propylene glycol methyl ether acetate 68.5g.
Wherein, the macromolecule resin is with construction unitResin, wherein, number of repeat unit
For 85；The small-molecular-weight resin has general structureWherein, number of repeat unit 16.
The preparation method of the photoresist comprises the following steps that：Above-mentioned each component is mixed, fully after dissolving, with 0.02 μm
The membrane filtration in aperture, that is, obtain photoresist.
The photoetching process of the photoresist comprises the following steps that：The above-mentioned photoresist of spin coating, is used in combination on the silicon chip through processing
Hot plate preliminary drying, in 100 DEG C of preliminary drying 90s；Regulation spin coating rotating speed makes dried photoresist thickness be 2.5 μm, through mask, passes through
After exposure machine i line ultraviolet photoetchings, photoresist reacts；Soaked with the aqueous solution of 2.38wt% TMAH
Bubble development 60s, after then being cleaned with deionized water, with post bake is dried after baking oven, 120s is dried in 120 DEG C, that is, completes photoetching process,
Obtain and mask shading region identical figure.
Embodiment 2
The composition of the photoresist of the present embodiment is：
Macromolecule resin 18.72g, small-molecular-weight resin 4.68g, 2,1,5- diazonium naphthoquinone sulphonate 6.6g, the Chinese Academy of Sciences
KH-550 1g, propylene glycol methyl ether acetate 69g.
Wherein, the macromolecule resin is with construction unitResin, wherein, repeat single
First number is 50；The small-molecular-weight resin has general structureWherein, number of repeat unit 9.
The preparation method of the photoresist comprises the following steps that：Above-mentioned each component is mixed, fully after dissolving, with 0.02 μm
The membrane filtration in aperture, that is, obtain photoresist.
The photoetching process of the photoresist comprises the following steps that：The above-mentioned photoresist of spin coating, is used in combination on the silicon chip through processing
Hot plate preliminary drying, in 100 DEG C of preliminary drying 90s；Regulation spin coating rotating speed makes dried photoresist thickness be 2.5 μm, through mask, passes through
After exposure machine i line ultraviolet photoetchings, photoresist reacts；Soaked with the aqueous solution of 2.38wt% TMAH
Bubble development 60s, after then being cleaned with deionized water, with post bake is dried after baking oven, 120s is dried in 120 DEG C, that is, completes photoetching process,
Obtain and mask shading region identical figure.
Embodiment 3
The composition of the photoresist of the present embodiment is：
Macromolecule resin 17.01g, small-molecular-weight resin 7.29g, 2,1,4- diazonium naphthoquinone sulphonate 5.7g, DOW CORNING
Z-6011 1.5g, propylene glycol methyl ether acetate 68.5g.
Wherein, the macromolecule resin is with construction unitResin, wherein, number of repeat unit
For 85；The small-molecular-weight resin has general structureWherein, number of repeat unit 9.
The preparation method of the photoresist comprises the following steps that：Above-mentioned each component is mixed, fully after dissolving, with 0.02 μm
The membrane filtration in aperture, that is, obtain photoresist.
The photoetching process of the photoresist comprises the following steps that：The above-mentioned photoresist of spin coating, is used in combination on the silicon chip through processing
Hot plate preliminary drying, in 100 DEG C of preliminary drying 90s；Regulation spin coating rotating speed makes dried photoresist thickness be 2.5 μm, through mask, passes through
After exposure machine i line ultraviolet photoetchings, photoresist reacts；Soaked with the aqueous solution of 2.38wt% TMAH
Bubble development 60s, after then being cleaned with deionized water, with post bake is dried after baking oven, 120s is dried in 120 DEG C, that is, completes photoetching process,
Obtain and mask shading region identical figure.
Embodiment 4
The composition of the photoresist of the present embodiment is：
Macromolecule resin 19.36g, small-molecular-weight resin 4.84g, 2,1,5- diazonium naphthoquinone sulphonate 5.8g, U.S.'s connection
Carbon company A-1100 1g, propylene glycol methyl ether acetate 69g.
Wherein, the macromolecule resin is with construction unitResin, wherein, repeat single
First number is 50；The small-molecular-weight resin has general structureWherein, number of repeat unit 16.
The preparation method of the photoresist comprises the following steps that：Above-mentioned each component is mixed, fully after dissolving, with 0.02 μm
The membrane filtration in aperture, that is, obtain photoresist.
The photoetching process of the photoresist comprises the following steps that：The above-mentioned photoresist of spin coating, is used in combination on the silicon chip through processing
Hot plate preliminary drying, in 100 DEG C of preliminary drying 90s；Regulation spin coating rotating speed makes dried photoresist thickness be 2.5 μm, through mask, passes through
After exposure machine i line ultraviolet photoetchings, photoresist reacts；Soaked with the aqueous solution of 2.38wt% TMAH
Bubble development 60s, after then being cleaned with deionized water, with post bake is dried after baking oven, 120s is dried in 120 DEG C, that is, completes photoetching process,
Obtain and mask shading region identical figure.
Embodiment 5
The composition of the photoresist of the present embodiment is：
Macromolecule resin 18.1g, small-molecular-weight resin 5.4g, 2,1,4- diazonium naphthoquinone sulphonate 6.5g, U.S.'s connection carbon
Company A-1100 1.5g, propylene glycol methyl ether acetate 68.5g.
Wherein, the macromolecule resin is with construction unitResin, wherein, number of repeat unit
For 85；The small-molecular-weight resin has general structureWherein, the R1For H or CH3, wherein, repeat
Unit number is 11.
The preparation method of the photoresist comprises the following steps that：Above-mentioned each component is mixed, fully after dissolving, with 0.02 μm
The membrane filtration in aperture, that is, obtain photoresist.
The photoetching process of the photoresist comprises the following steps that：The above-mentioned photoresist of spin coating, is used in combination on the silicon chip through processing
Hot plate preliminary drying, in 100 DEG C of preliminary drying 90s；Regulation spin coating rotating speed makes dried photoresist thickness be 2.5 μm, through mask, passes through
After exposure machine i line ultraviolet photoetchings, photoresist reacts；Soaked with the aqueous solution of 2.38wt% TMAH
Bubble development 60s, after then being cleaned with deionized water, with post bake is dried after baking oven, 120s is dried in 120 DEG C, that is, completes photoetching process,
Obtain and mask shading region identical figure.
Embodiment 6
The composition of the photoresist of the present embodiment is：
Macromolecule resin 17.65g, small-molecular-weight resin 5.3g, 2,1,4- diazonium naphthoquinone sulphonate 7.05g, U.S.'s connection
Carbon company A-1100 1.5g, propylene glycol methyl ether acetate 68.5g.
Wherein, the macromolecule resin is with construction unitResin, wherein, number of repeat unit is
92, the R1For H or CH3；The small-molecular-weight resin has general structureWherein, number of repeat unit
For 16.
The preparation method of the photoresist comprises the following steps that：Above-mentioned each component is mixed, fully after dissolving, with 0.02 μm
The membrane filtration in aperture, that is, obtain photoresist.
The photoetching process of the photoresist comprises the following steps that：The above-mentioned photoresist of spin coating, is used in combination on the silicon chip through processing
Hot plate preliminary drying, in 100 DEG C of preliminary drying 90s；Regulation spin coating rotating speed makes dried photoresist thickness be 2.5 μm, through mask, passes through
After exposure machine g line ultraviolet photoetchings, photoresist reacts；Soaked with the aqueous solution of 2.38wt% TMAH
Bubble development 60s, after then being cleaned with deionized water, with post bake is dried after baking oven, 120s is dried in 120 DEG C, that is, completes photoetching process,
Obtain and mask shading region identical figure.
Embodiment 7
The composition of the photoresist of the present embodiment is：
Macromolecule resin 15g, small-molecular-weight resin 2g, 2,1,4- diazonium naphthoquinone sulphonate 3g, union carbide corporation of U.S. A-
1100 1g, propylene glycol methyl ether acetate 79g.
Wherein, the macromolecule resin is with construction unitResin, wherein, number of repeat unit is
92, the R1For H or CH3；The small-molecular-weight resin has general structureWherein, number of repeat unit
For 16.
The preparation method of the photoresist comprises the following steps that：Above-mentioned each component is mixed, fully after dissolving, with 0.02 μm
The membrane filtration in aperture, that is, obtain photoresist.
The photoetching process of the photoresist comprises the following steps that：The above-mentioned photoresist of spin coating, is used in combination on the silicon chip through processing
Hot plate preliminary drying, in 100 DEG C of preliminary drying 90s；Regulation spin coating rotating speed makes dried photoresist thickness be 2.5 μm, through mask, passes through
After exposure machine g line ultraviolet photoetchings, photoresist reacts；Soaked with the aqueous solution of 2.38wt% TMAH
Bubble development 60s, after then being cleaned with deionized water, with post bake is dried after baking oven, 120s is dried in 120 DEG C, that is, completes photoetching process,
Obtain and mask shading region identical figure.
Embodiment 8
The composition of the photoresist of the present embodiment is：
Macromolecule resin 25g, small-molecular-weight resin 16g, 2,1,4- diazonium naphthoquinone sulphonate 7.5g, union carbide corporation of the U.S.
A-1100 1.5g, propylene glycol methyl ether acetate 50g.
Wherein, the macromolecule resin is with construction unitResin, wherein, number of repeat unit is
92, the R1For H or CH3；The small-molecular-weight resin has general structureWherein, number of repeat unit
For 16.
The preparation method of the photoresist comprises the following steps that：Above-mentioned each component is mixed, fully after dissolving, with 0.02 μm
The membrane filtration in aperture, that is, obtain photoresist.
The photoetching process of the photoresist comprises the following steps that：The above-mentioned photoresist of spin coating, is used in combination on the silicon chip through processing
Hot plate preliminary drying, in 100 DEG C of preliminary drying 90s；Regulation spin coating rotating speed makes dried photoresist thickness be 2.5 μm, through mask, passes through
After exposure machine g line ultraviolet photoetchings, photoresist reacts；Soaked with the aqueous solution of 2.38wt% TMAH
Bubble development 60s, after then being cleaned with deionized water, with post bake is dried after baking oven, 120s is dried in 120 DEG C, that is, completes photoetching process,
Obtain and mask shading region identical figure.
Comparative example 1
The composition of photoresist for comparing is：
Macromolecule resin 22.95g, 2,1,4- diazonium naphthoquinone sulphonate 7.05g, surfactant 1.5g, propane diols first
Ether acetate 68.5g.
Wherein, the macromolecule resin is with construction unitResin, wherein, number of repeat unit is
92, the R1For H or CH3。
The preparation method of the photoresist of comparative example is similar with the preparation method of the present invention, comprises the following steps that：Will be above-mentioned each
Component mixes, and fully after dissolving, with the membrane filtration in 0.02 μm of aperture, that is, obtains the photoresist of comparative example.
With reference to the photoetching process of the present invention, the photoresist of the above-mentioned comparative example of spin coating on the silicon chip through processing, and use hot plate
Preliminary drying, in 100 DEG C of preliminary drying 90s；Regulation spin coating rotating speed makes dried photoresist thickness be 2.5 μm, through mask, passes through exposure
After machine i line ultraviolet photoetchings, immersion development 60s is carried out with the aqueous solution of 2.38wt% TMAH, is then spent
After ionized water cleaning, with post bake is dried after baking oven, 120s is dried in 120 DEG C, completes photoetching.
Experimental example 1
For the photoresist and the photoresist of comparative example described in the embodiment of the present invention, the performance after development is contrasted, tool
Body, be respectively in the silica of same treatment condition by the photoresist described in the embodiment of the present invention and the photoresist of comparative example
Spin coating photoresist on piece, hot plate preliminary drying, in 100 DEG C of preliminary drying 90s；Regulation spin coating rotating speed makes dried photoresist thickness be 2.5 μ
M, through mask, after exposure machine i line ultraviolet photoetchings, soaked with the aqueous solution of 2.38wt% TMAH
Bubble development 60s, after then being cleaned with deionized water, with post bake is dried after baking oven, 120s is dried in 120 DEG C.To the embodiment of the present invention
Pattern after described photoresist and the photoresist developing of comparative example is taken pictures, please refer to Fig. 1, Fig. 2 and Fig. 3, its point
Be not the present invention photoresist development effect figure, development after the photoresist of sectional view and comparative example development effect figure.From figure
In understand, photoresist of the invention is by introducing small-molecular-weight resin, and the compactness of structure, is improved viscous after increase photoresist baking
Attached power, improve drift glue situation.
Experimental example 2
For the photoresist and the photoresist of comparative example described in the embodiment of the present invention, the performance after wet etching is carried out pair
Than specifically, being respectively the two of same treatment condition by the photoresist described in the embodiment of the present invention and the photoresist of comparative example
Spin coating photoresist on oxidized silicon chip, hot plate preliminary drying, in 100 DEG C of preliminary drying 90s；Regulation spin coating rotating speed makes dried photoresist thickness
For 2.5 μm, through mask, after exposure machine i line ultraviolet photoetchings, with the aqueous solution of 2.38wt% TMAH
Immersion development 60s is carried out, after then being cleaned with deionized water, with post bake is dried after baking oven, 120s is dried in 120 DEG C.Carry out wet method
Etching.Etching solution is BOE (HF+NH4F, the HF aqueous solution and NH4The volume ratio of the F aqueous solution is 1 ﹕ 6), normal temperature condition etching 10min,
Pattern after being etched to the photoresist of the photoresist described in the embodiment of the present invention and comparative example is taken pictures, please refer to Fig. 4
And Fig. 5, it is the etching section design sketch of the photoresist for etching section design sketch and comparative example of the photoresist of the present invention respectively.
It can be seen that the photoresist of the present invention, by introducing small-molecular-weight resin, the compactness of structure, is carried after increase photoresist baking
High adhesion, improve etched side corruption situation.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of photoresist, it is characterised in that be mainly made up of macromolecule resin, small-molecular-weight resin, sensitising agent and solvent；
Preferably, the photoresist is mainly made up of following components by mass percentage：
Macromolecule resin 15-25%, small-molecular-weight resin 2-16%, sensitising agent 3-15% and solvent 50-80%.
2. photoresist according to claim 1, it is characterised in that the molecular weight ranges of the small-molecular-weight resin are
1000-3000, the molecular weight of the macromolecule resin is 7000-12000.
3. photoresist according to claim 1, it is characterised in that the small-molecular-weight resin is including general structureResin in one or more；Wherein, n1For 7-
22 integer, n2For 8-25 integer, n3For 6-20 integer；R1、R2And R3For hydrogen or alkyl.
4. photoresist according to claim 1, it is characterised in that the macromolecule resin includes phenolic resin, had
Construction unitResin, there is construction unitResin and there is construction unitResin in one or more.
5. according to the photoresist described in claim any one of 1-4, it is characterised in that the small-molecular-weight resin accounts for macromolecule
The mass percent of resin is 20-60%；
Preferably, the mass percent that the small-molecular-weight resin accounts for macromolecule resin is 30-40%.
6. photoresist according to claim 5, it is characterised in that the sensitising agent includes diphenyl iodine hexafluorophosphoric acid
Ester, diphenyl iodine trifluoromethayl sulfonic acid ester, the fluorine n-butanesulfonic acid ester of diphenyl iodine nine, diphenyl iodine perfluoro-n-octane sulphur
Acid esters, diphenyl iodine camphorsulfonic acid ester, double (4- tert-butyl-phenyls) iodine camphorsulfonic acid esters, double (4- tert-butyl-phenyls) iodine
Trifluoromethayl sulfonic acid ester, double (trifluoromethyl sulfonyl) diazomethanes, 2,1,4- diazonium naphthoquinone sulphonates, 2,1,5- diazo naphthoquinones
In sulphonic acid ester, 2,3,4- trihydroxybenzophenones, the nitrine -4- sulfonic acid of 1,2- benzoquinones two and the nitrine -5- sulfonic acid of 1,2- naphthoquinones two
It is one or more；
Preferably, the solvent includes the solvent that can dissolve the macromolecule resin, small-molecular-weight resin and sensitising agent；
It is furthermore preferred that the solvent includes diethyl carbonate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate
Ester, n-butyl acetate, isobutyl acetate, methyl cyclohexyl ester, n-nonyl acetate, methyl acetoacetate, acetoacetate second
Ester, glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetate, the third two
Alcohol phenylate acetate, ethylene acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, methyl lactate, ethyl lactate,
N-butyl lactate, N_amyl lactate, diethyl malonate, repefral, diethyl phthalate, N- methyl first
Acid amides, DMF, N, N- diethylformamides, acetamide, N- methylacetamides, DMA,
N- methyl propanamides, 1-METHYLPYRROLIDONE, dimethyl disulfide, diethyl sulfide, thiophene, thiophane, dimethyl sulfoxide (DMSO), ring fourth
Sulfone, 1,3- propane sultones, methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, pentane, isopentane, n-hexane,
In isohexane, normal heptane, benzene,toluene,xylene, acetone, methyl ethyl ketone, ethylene glycol, propane diols, ether and ethylene glycol ethyl ether
One or more.
7. the preparation method of the photoresist described in claim any one of 1-6, it is characterised in that comprise the following steps：By each group
After dividing mixed dissolution, photoresist is filtrated to get；
Preferably, with 0.02 μm and the membrane filtration in following aperture.
8. the photoetching process of the photoresist described in claim any one of 1-6, it is characterised in that comprise the following steps：By described in
Photoresist is applied to substrate surface, and preliminary drying is dried, and development is soaked after ultraviolet photoetching, dries post bake after then cleaning substrate.
9. the photoetching process of photoresist according to claim 8, it is characterised in that the temperature that the preliminary drying is dried is 90-
110 DEG C, the time that the preliminary drying is dried is 60-150s；
Preferably, the temperature for drying post bake is 115-125 DEG C, and the time for drying post bake is 90-180s.
10. the photoetching process of photoresist according to claim 8, it is characterised in that the ultraviolet light be g lines ultraviolet light or
I line ultraviolet lights.
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| CN110632808A (en) * | 2018-06-25 | 2019-12-31 | 蓝思科技（长沙）有限公司 | Method for disassembling and degumming sapphire wafer and metal part |
| WO2022033366A1 (en) * | 2020-08-13 | 2022-02-17 | 无锡华睿芯材科技有限公司 | Photoresist composition, method for using same to form lithographic pattern, and uses of same |
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