CN101149561A - Main body film forming resin for photoresist and its preparation method and uses - Google Patents
Main body film forming resin for photoresist and its preparation method and uses Download PDFInfo
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- CN101149561A CN101149561A CNA2007100536663A CN200710053666A CN101149561A CN 101149561 A CN101149561 A CN 101149561A CN A2007100536663 A CNA2007100536663 A CN A2007100536663A CN 200710053666 A CN200710053666 A CN 200710053666A CN 101149561 A CN101149561 A CN 101149561A
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Abstract
There is a sort of principal phragmoid colophony that it is used for the light-sensitive lacquer, and its manufacturing method is that 1. Make the monomer N-substitution methyl radical acrylamide and the monomer N-substitution maleimide to be dissolved to the solvent in order to execute the homogeneous liquor. 2. Affiliate the free-radical polymerization initiator in this liquor, and aggregate them in the definite temperature, and then drop it to the precipitator in order to separate out the polymer deposition, at last filtrate it, and then get the coarse production. 3. Dissolve this coarse production in the solvent anew, and then drop it to the precipitator in order to deposition, at last filtrate it, and then get the copolymer colophony of this invention. Its applied method is that: Dissolve the copolymer colophony and the sensitizer and the additive and the solvent, and filtrate it by the hyper-filtration membrane, at last get the light-sensitive lacquer of this invention. This light-sensitive lacquer has the character in that the high resolution factor, the good adhesive power with the bulk material, and the strong anti-dry-etching ability. In addition it has the good high-temperature capability.
Description
Technical field
A kind of main body film-forming resin that is used for photoresist and its production and application, what be particularly related to is in the microelectronics manufacture process, the main body film-forming resin N-substituent methyl acrylamide of required photoresist and multipolymer of N-substituted maleimide amine and its production and application.
Background technology
Photoresist (Photoresist) claims photoresist again, is meant irradiation or irradiation by ultraviolet light, electron beam, the particle beams, x-ray etc., the anticorrosion film material that its solubleness changes.Photoresist is to finish the key basic material that microelectronics is made photoetching process, and it is determining the development level of microelectric technique.Photoresist is made up of film-forming resin, emulsion, solvent and some adjuvants usually, and its most important two performances are sensitivity and resolution, and the anti-dry ecthing ability of photoresist is also very important in addition.Different according to exposure light source and radiation source, photoresist can be divided into ultraviolet photoresist, deep ultraviolet light-sensitive lacquer (248nm photoresist), extreme ultraviolet photolithographic glue (comprising 193nm and 157nm photoresist), electron beam adhesive, particle beams glue and x-ray glue etc.
The main body film-forming resin is one of main composition of photoresist, and its performance quality has decisive influence to the photoresist performance, and it is the skeleton of photoresist, is the basic material of photoresist.For the main body film-forming resin, its main performance requirement comprises:
1. the dissolubility of resin in photoresist solvent commonly used will be got well, easily film forming;
2. the functional group such as hydroxyl, carbonyl that should contain suitable quantity in the resin structure makes base materials such as itself and monocrystalline silicon piece that good bonding force be arranged; Contain the aromatic ring of right quantity or alicyclic ring etc., make its have good plasma resistant etch capabilities (at least should with linear phenolic resin quite);
3. for the film-forming resin that is used for different exposure wavelengths, its ultraviolet light to specific wavelength will have good permeability, and (optical density (OD) is less than 0.45 μ m
-1).
The linear phenolic resin base polymer still is widely used as the film-forming resin of ultraviolet g-line (436nm), i-line (365nm) even deep ultraviolet (248nm) photoresist at present, but the glass temperature (T of linear phenolic resin
g) lower [with the difference of polymer molecular weight, between 70～120 ℃ (Pro.SPIE, Vol.2438, pp.40～52,1995)], there is the shortcoming of thermotolerance deficiency.And present some hot environments in the microelectronic processing technology as multilevel resist system, ion implantation technique etc., just require the photoresist figure indeformable under 200 ℃ even higher temperature; Simultaneously in the chemical amplification type photoresist, high T
gThe migration of resin catalyzer (proton) can reduce in the photoetching baking time, improve the resolution of photoresist.
In order to improve the T of main body film-forming resin
gAs far back as 1986, (Polym.Eng.Sci., Vol.26, No.16 such as S.Rechard Turner, 1986) prepared the film-forming resin of the alternating copolymer of the maleimide derivatives that a series of alkene and N-replace as photoresist, (J.Polym.Sci.:Part A:Polym.Chem., Vol.29, pp.399～410 such as Chiang, 1991) also synthesized siliceous resin system, the T of these film-forming resins
gReach as high as 250 ℃, its structural formula is respectively shown in I and II.
(R=H, C
6H
5, C
6H
5OH etc.) (R=H, C
6H
5, C
6H
5OH etc.
(formula I) (formula II)
The present invention has prepared a class and has had higher T
gThe amide-imide multipolymer, from present gained document, do not see that it is used as the report of photoresist main body film-forming resin.
Summary of the invention
The present invention hangs down the shortcoming that reaches the thermotolerance deficiency for the photoresist main body film-forming resin glass temperature that overcomes prior art, has prepared the copolymer resin of N-substituent methyl acrylamide and N-substituted maleimide amine.
The copolymer resin of N-substituent methyl acrylamide of the present invention and N-substituted maleimide amine has following structural unit:
R in the formula
1=H, NH
2, OH, COOH, OOCCH
3Or COOCCH
3, R
2=OH, H, NH
2, COOH, OOCCH
3Or COOCCH
3
The number-average molecular weight of this fluoropolymer resin is 1 * 10
2～1 * 10
8Between, the molecular weight distribution coefficient is between 1～6, and glass temperature is more than 255 ℃.
The preparation method of above-mentioned copolymer resin is:
(1) monomer N-substituent methyl acrylamide and monomer N-substituted maleimide amine are dissolved in one of following solvent by 1/0～100 mol ratio: acetone, carbon disulphide, tetrahydrofuran (THF), dioxane, N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO), toluene or acetonitrile, make homogeneous phase solution, the weight ratio of monomer whose and solvent is 1/10～15;
(2) 0.01%～20% of the adding total monomer weight azoisobutyronitrile (AIBN) or dibenzoyl peroxide (BPO) are radical polymerization initiator in above-mentioned solution, vacuumize deoxygenation, and use nitrogen protection, and under 50～100 ℃ of conditions of temperature, static or stirring polymerization 24～72h, (precipitation agent is ether, methyl alcohol, water or ethanol in the slow then impouring precipitation agent, its volume is 1～10 times of solvent), separate out polymer precipitation, suction filtration, vacuum drying gets crude product;
(3) this crude product is dissolved in one of following solvent again: acetone, carbon disulphide, tetrahydrofuran (THF), dioxane, N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO), toluene or acetonitrile, the weight ratio of monomer whose and solvent is 1/10～15; With (precipitation agent is ether, methyl alcohol, water or ethanol, and its volume is 1～10 times of solvent) in the slow impouring precipitation agent of the solution for preparing, precipitate suction filtration, 65 ℃ of vacuum drying, three times repeatedly, the copolymer resin that obtains purifying again.
The application process of copolymer resin of the present invention in the photoresist preparation is:
With copolymer resin and emulsion: the diazo naphthoquinone sulfonic acid chloride; Adjuvant: benzophenone; One of following solvent: after cyclohexanone, ethylene glycol monoethyl ether or N, dinethylformamide (DMF) 5～40: 1.5～12: 1～8.4: 100 preparations by weight proportion, promptly make photoresist of the present invention through ultrafiltration membrance filter.
This photoresist filming performance is good, and (as Wafer) has good bonding force with matrix, its anti-dry ecthing ability and linear phenolic resin quite, especially it has very outstanding high temperature resistance.
Present invention focuses on to have solved following problem:
Other related component of high molecular polymer among the present invention and photoresist is composite, can obtain photoresist, this photoresist except that have the resolution height, with good, the anti-dry ecthing ability of matrix material adhesion by force, have more fabulous resistance to elevated temperatures, can satisfy up to the microelectronic processing technology temperature more than 255 ℃, and keep the photoresist figure indeformable.
Embodiment
Example 1: monomer N-phenyl methyl acrylamide and monomer N-phenylmaleimide are dissolved in dioxane (W/W: 1/10) by 1: 1 mol ratio; make homogeneous phase solution, 1% the AIBN that adds total monomer weight is a radical polymerization initiator, vacuumizes deoxygenation; and use nitrogen protection; under 65 ℃ of conditions of constant temperature, static polymerization 24h is in the slow then impouring precipitation agent ether; separate out polymer precipitation; suction filtration, vacuum drying gets crude product.This crude product is dissolved in dioxane (W/W: 1/10), in the slow again impouring ether (its volume is 9 times of used dioxane volume), precipitate suction filtration, 65 ℃ of vacuum drying, three times repeatedly, the copolymer resin that obtains purifying again.
With this copolymer resin and diazo naphthoquinone sulfonic acid chloride, benzophenone and cyclohexanone (W/W, 5: 1.6: 2: after 100) composite, promptly can be made into photoresist in proportion through ultrafiltration membrance filter.
Example 2: monomer N-(p-acetoxyl group phenyl) Methacrylamide and monomer N-(p-hydroxy phenyl) maleimide are dissolved in DMSO (W/W: 1/13) by 1: 50 mol ratio; make homogeneous phase solution, 10% the BPO that adds total monomer weight is a radical polymerization initiator, vacuumizes deoxygenation; and use nitrogen protection; under 70 ℃ of conditions of constant temperature, stir polymerization 48h, in the slow then impouring precipitation agent water; separate out polymer precipitation; suction filtration, vacuum drying gets crude product.With this crude product be dissolved in again DMSO (W/W: 1/13), more slowly in the impouring water (its volume is 5 times of DMSO), suction filtration, 65 ℃ of vacuum drying, three times repeatedly, the copolymer resin that obtains purifying.
With this copolymer resin and diazo naphthoquinone sulfonic acid chloride, benzophenone and ethylene glycol monoethyl ether, (W/W, 20: 8: 5: after 100) composite, promptly can be made into photoresist in proportion through ultrafiltration membrance filter.
Example 3: monomer N-(p-acetoxyl group phenyl) Methacrylamide and monomer N-(p-hydroxy phenyl) maleimide are dissolved in DMF (W/W: 1/15) by 1: 90 mol ratio; make homogeneous phase solution, 19% the BPO that adds total monomer weight is a radical polymerization initiator, vacuumizes deoxygenation; and use nitrogen protection; under 75 ℃ of conditions of constant temperature, stir polymerase 17 2h, in the slow then impouring precipitation agent water; separate out polymer precipitation; suction filtration, vacuum drying gets crude product.With this crude product be dissolved in again DMF (W/W: 1/15), more slowly in the impouring water (its volume is 1 times of DMSO), suction filtration, 65 ℃ of vacuum drying, three times repeatedly, the copolymer resin that obtains purifying.
With this copolymer resin and diazo naphthoquinone sulfonic acid chloride, benzophenone and ethylene glycol monoethyl ether, (W/W, 40: 12: 8: after 100) composite, promptly can be made into photoresist in proportion through ultrafiltration membrance filter.
Example 4: monomer N-(p-acetoxyl group phenyl) Methacrylamide and monomer N-(p-hydroxy phenyl) maleimide are dissolved in DMF (W/W: 1/11) by 1: 25 mol ratio; make homogeneous phase solution, 5% the AIBN that adds total monomer weight is a radical polymerization initiator, vacuumizes deoxygenation; and use nitrogen protection; under 65 ℃ of conditions of constant temperature, stir polyase 13 6h, in the slow then impouring precipitation agent water; separate out polymer precipitation; suction filtration, vacuum drying gets crude product.With this crude product be dissolved in again DMF (W/W: 1/11), more slowly in the impouring water (its volume is 4 times of DMSO), suction filtration, 65 ℃ of vacuum drying, three times repeatedly, the copolymer resin that obtains purifying.
With this copolymer resin and diazo naphthoquinone sulfonic acid chloride, benzophenone and ethylene glycol monoethyl ether, (W/W, 15: 5: 3.5: after 100) composite, promptly can be made into photoresist in proportion through ultrafiltration membrance filter.
Example 5: monomer N-(p-acetoxyl group phenyl) Methacrylamide and monomer N-(p-hydroxy phenyl) maleimide are dissolved in DMF (W/W: 1/14) by 1: 75 mol ratio; make homogeneous phase solution, 15% the BPO that adds total monomer weight is a radical polymerization initiator, vacuumizes deoxygenation; and use nitrogen protection; under 75 ℃ of conditions of constant temperature, stir polymerization 60h, in the slow then impouring precipitation agent water; separate out polymer precipitation; suction filtration, vacuum drying gets crude product.With this crude product be dissolved in again DMF (W/W: 1/14), more slowly in the impouring water (its volume is 7 times of DMSO), suction filtration, 65 ℃ of vacuum drying, three times repeatedly, the copolymer resin that obtains purifying.
With this copolymer resin and diazo naphthoquinone sulfonic acid chloride, benzophenone and ethylene glycol monoethyl ether, (W/W, 30: 10: 7: after 100) composite, promptly can be made into photoresist in proportion through ultrafiltration membrance filter.
Claims (4)
1. main body film-forming resin that is used for photoresist, it is characterized in that: this resin is the copolymer resin of N-substituent methyl acrylamide and N-substituted maleimide amine, and has following structural unit:
R in the formula
1=H, NH
2, OH, COOH, OOCCH
3Or COOCCH
3, R
2=OH, H, NH
2, COOH, OOCCH
3Or COOCCH
3
The number-average molecular weight of this copolymer resin is 1 * 10
2～1 * 10
8Between, the molecular weight distribution coefficient is between 1～6.
2. the preparation method of the described copolymer resin of claim 1, concrete steps are:
(1) monomer N-substituent methyl acrylamide and monomer N-substituted maleimide amine are dissolved in one of following solvent by 1/0～100 mol ratio: acetone, carbon disulphide, tetrahydrofuran, dioxane, N, dinethylformamide, dimethyl sulfoxide, toluene or acetonitrile are made homogeneous phase solution;
(2) in above-mentioned solution, add 0.01%～20% azoisobutyronitrile of total monomer weight or dibenzoyl peroxide as radical polymerization initiator, under 50～100 ℃ of conditions of temperature, static or stir polymerization 24～72h, in slow then ether, methyl alcohol, water or the ethanol of impouring as precipitation agent, separate out polymer precipitation, suction filtration, vacuum drying gets crude product;
(3) this crude product is dissolved in one of following solvent again: acetone, carbon disulphide, tetrahydrofuran, dioxane, N, dinethylformamide, dimethyl sulfoxide, toluene or acetonitrile, in slow then ether, methyl alcohol, water or the ethanol of impouring as precipitation agent, precipitation, suction filtration, 65 ℃ of vacuum drying, three times repeatedly, the copolymer resin that obtains purifying.
3. according to the preparation method of the described copolymer resin of claim 2, step (1) and the described monomer of step (3) and solvent are mixed with homogeneous phase solution, and the weight ratio of monomer whose and solvent is 1/10～15; Step (2) and the described precipitation agent of step (3), its volume are 1～10 times of the employed solvent of step (1).
4. the application process of the described copolymer resin of claim 1 in the photoresist preparation process is: with copolymer resin and emulsion: the diazo naphthoquinone sulfonic acid chloride; Adjuvant: benzophenone; One of following solvent: after cyclohexanone, ethylene glycol monoethyl ether or N, dinethylformamide 5～40: 1.5～12: 1～8.4: 100 preparations by weight proportion, promptly make photoresist of the present invention through ultrafiltration membrance filter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100536663A CN101149561A (en) | 2007-10-26 | 2007-10-26 | Main body film forming resin for photoresist and its preparation method and uses |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100536663A CN101149561A (en) | 2007-10-26 | 2007-10-26 | Main body film forming resin for photoresist and its preparation method and uses |
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|---|---|
| CN101149561A true CN101149561A (en) | 2008-03-26 |
Family
ID=39250144
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100536663A Pending CN101149561A (en) | 2007-10-26 | 2007-10-26 | Main body film forming resin for photoresist and its preparation method and uses |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102301279A (en) * | 2009-01-29 | 2011-12-28 | 日本电气株式会社 | Positive-type photosensitive insulating resin composition, and method for forming pattern using same |
| CN103360958A (en) * | 2013-07-16 | 2013-10-23 | 南昌欧菲光科技有限公司 | Adhesive and application thereof as well as adhesive film component and application thereof |
| CN104341551A (en) * | 2013-08-09 | 2015-02-11 | 三菱丽阳株式会社 | Method of manufacturing polymer for lithography, method of manufacturing resist composition, and method of manufacturing substrate having pattern |
| CN104641294A (en) * | 2012-10-02 | 2015-05-20 | 日产化学工业株式会社 | Negative photosensitive resin composition |
| CN112694555A (en) * | 2020-12-25 | 2021-04-23 | 苏州禾川化学技术服务有限公司 | Deep ultraviolet positive photoresist film-forming resin and preparation method thereof |
| CN112859523A (en) * | 2019-11-12 | 2021-05-28 | 台湾永光化学工业股份有限公司 | Polyimide positive photoresist composition |
-
2007
- 2007-10-26 CN CNA2007100536663A patent/CN101149561A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102301279A (en) * | 2009-01-29 | 2011-12-28 | 日本电气株式会社 | Positive-type photosensitive insulating resin composition, and method for forming pattern using same |
| CN102301279B (en) * | 2009-01-29 | 2013-07-17 | 日本电气株式会社 | Positive-type photosensitive insulating resin composition, and method for forming pattern using same |
| CN104641294A (en) * | 2012-10-02 | 2015-05-20 | 日产化学工业株式会社 | Negative photosensitive resin composition |
| CN104641294B (en) * | 2012-10-02 | 2019-08-23 | 日产化学工业株式会社 | Negative light-sensitive resin combination |
| CN103360958A (en) * | 2013-07-16 | 2013-10-23 | 南昌欧菲光科技有限公司 | Adhesive and application thereof as well as adhesive film component and application thereof |
| CN104341551A (en) * | 2013-08-09 | 2015-02-11 | 三菱丽阳株式会社 | Method of manufacturing polymer for lithography, method of manufacturing resist composition, and method of manufacturing substrate having pattern |
| CN104341551B (en) * | 2013-08-09 | 2017-06-09 | 三菱丽阳株式会社 | The manufacture method of the manufacture method of lithographic printing polymer, the manufacture method of anti-corrosion agent composition and the figuratum substrate of formation |
| CN112859523A (en) * | 2019-11-12 | 2021-05-28 | 台湾永光化学工业股份有限公司 | Polyimide positive photoresist composition |
| CN112859523B (en) * | 2019-11-12 | 2024-04-26 | 台湾永光化学工业股份有限公司 | Polyimide positive photoresist composition |
| CN112694555A (en) * | 2020-12-25 | 2021-04-23 | 苏州禾川化学技术服务有限公司 | Deep ultraviolet positive photoresist film-forming resin and preparation method thereof |
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Open date: 20080326 |