CN101364055B - Neutral developer solution for positive light-sensitive polyimides photo resist - Google Patents
Neutral developer solution for positive light-sensitive polyimides photo resist Download PDFInfo
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- CN101364055B CN101364055B CN2008100460781A CN200810046078A CN101364055B CN 101364055 B CN101364055 B CN 101364055B CN 2008100460781 A CN2008100460781 A CN 2008100460781A CN 200810046078 A CN200810046078 A CN 200810046078A CN 101364055 B CN101364055 B CN 101364055B
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Abstract
The invention relates to a neutral developing solution used for a positive photo-sensitive polyimide photoresist, which belongs to the material technical field and relates to the field of photolithographic techniques, particularly the developing techniques in photolithography. The neutral developing solution used for positive photo-sensitive polyimide photoresists is composed of the following components: 30.0-60.0wt% of a water-soluble amide compound, 1.0-10.0wt% of a water-soluble alcohol or alcohol ether compound, 0.01-3.0wt% of a non-ionic surfactant and water in balance. The pH value of the photoresists is in the range from 6.5 to 7.5. The neutral developing solution increases the difference in solubility between the exposure region and the non-exposure region of the positive photo-sensitive polyimide photoresist in the neutral developing solution, enables the exposure region to rapidly and completely dissolve while the non-exposure region hardly soluble, and ensures sharp line and clear outline of the photolithographic pattern. The water-soluble alcohol or alcohol ether compound has stable dispersibility and defoaming and solution-supporting functions, so that the developing solution has excellent dispersion stability and defoaming property. The neutral developing solution is particularly applicable to the photolithographic process of the positive photo-sensitive polyimide photoresist on the alkali-sensitive substrate or functional film.
Description
Technical field
The neutral developer solution of positive light-sensitive polyimides photoresist belongs to the material technology field, relates to making photoetching process, especially the developing technique in the photoetching process.
Background technology
In device technologies such as semiconductor, photoelectron and microelectronics, solution or colloidal sol that people Chang Shouxian will contain photosensitive resin are coated on the substrate, film with the rayed of certain wavelength then, thus at last with appropriate solvent or solution with the illumination part or not be partly dissolved by illumination to remove to obtain figure.These three steps are called gluing, exposure and development, and whole process is called photoetching or graphical.The solvent or the solution that use during development are called developer solution, and the solution that contains photosensitive resin or the colloidal sol that use during gluing are called photoresist.Dissolving is removed when developing be illumination partly or be not subjected to the illumination part, photoresist is called positive photoresist and negative photoresist.Positive photoresist is higher because of resolution, available water solution develops more can satisfy the micro-processing technology and the environmental requirement of high speed development, is subjected to paying attention to widely, develops also rapider.
In traditional device technology, graphical polymer coating film will all be removed after the relevant subsequent operation is finished, and therefore thermal behavior and the electrical property to photosensitive resin do not have specific (special) requirements.But along with developing rapidly of micro-processing technology, people have proposed the minimizing operation, thereby the new technology that need not to remove graphical polymer coating film that improve precision, reduces cost, this has just proposed special requirement such as high heat-resisting, high insulation, low-k to photosensitive resin, the positive photoresist of types such as traditional novolac resin, acryl resin, maleic acid resin and epoxy resin can not satisfy this requirement, and the positive light-sensitive polyimides photoresist arises at the historic moment in this case.
Wish to get meticulous, litho pattern clearly, the performance and the quality of photoresist have crucial effects, and Dui Ying developer solution also has vital role with it.Desirable positive photoresist should be can quick and complete dissolving exposed portion and dissolve the solvent or the solution of unexposed portion hardly with developer solution.Existing positive photoresist all is (the Chinese patent 02156178.8,02827572.1,02827571.3,200510006257.9,200510052183.2,200480025098.0,200510098603.0,200510101307.1,200610138251.1,200680021234.8 that proposes at the positive photoresist of types such as novolac resin, acryl resin, maleic acid resin and epoxy resin with developer solution; Japanese patent laid-open 5-88377, spy open flat 6-109916, spy and open flat 10-213908, spy and open flat 10-26826, spy and open flat 10-161304, spy and open flat 10-90881, spy and open 2003-337409, spy and open 2004-102062, spy and open that flat 6-308316, spy open flat 7-120935, the spy opens flat 9-34128), when these developer solutions are used for the positive light-sensitive polyimides photoresist, the ubiquity exposed portion can not dissolve fully, thereby the defective that residue occurs, these residues make figure blur even further influence the electrical property of device.And these developer solutions all are alkalescence even alkaline, if deposited some not alkaline-resisting functional membrane on the substrate, alkaline-based developer will damage the functional of functional membrane.Such as, in the manufacturing process of device of non-refrigerated infrared focal plane array, need on vanadium oxide film, utilize positive light-sensitive polyimides photoresist etching figure, if use alkalescence even alkalescent developing liquid developing all will destroy the sensitivity characteristic of vanadium oxide film, even all will change the valence state structure of barium oxide because the pH value is 8.0 weak base, can only use neutral developer solution this moment.Yet do not see the bibliographical information of any relevant positive light-sensitive polyimides photoresist so far with neutral developer solution.
Summary of the invention
The invention provides the neutral developer solution of a kind of positive light-sensitive polyimides photoresist.
The present invention finds when the dissolubility of research polyimide and presoma thereof, containing the polyimide of adjacent diazo naphthoquinone photosensitive group and presoma thereof, to be lower than in the amide aqueous solution of 65wt% at content almost be insoluble, has fine solubility and contain the polyimide of the indenes acid groups that adjacent diazo naphthoquinone exposure back forms and presoma thereof in content is higher than the amide aqueous solution of 30wt%.This important discovery makes the inventor finish the present invention just.
The neutral developer solution of positive light-sensitive polyimides photoresist provided by the invention, its component comprises the water-soluble amide compounds of 30.0～60.0wt%, water-soluble alcohol or pure ether compound, the non-ionic surfactant of 0.01～3.0wt% and the water of surplus of 1.0～10.0wt%, and its pH value is between 6.5～7.5.
Described water-soluble amide compounds is a formamide, acetamide (ACA), propionamide (PRA), butyramide, isobutyramide, N, dinethylformamide (DMF), N, the N-diethylformamide, N, N-dimethyl acetamide (DMAC), N, the N-diethyl acetamide, N-Methyl pyrrolidone, N-ethyl pyrrolidone or their composition, preferred acetamide, propionamide, butyramide, isobutyramide, N, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP) or their composition, N most preferably, N-dimethyl acetamide (DMAC), N, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP) or their composition.
The preferred content of described water-soluble amide compounds is 35.0～55.0wt%, and most preferred content is 40.0～50.0wt%.Described water-soluble alcohol or pure ether compound are methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or their composition, particular methanol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutyl alcohol, sec-butyl alcohol, the tert-butyl alcohol or their composition, most preferred ethanol, propyl alcohol, isopropyl alcohol or their composition.
The preferred content of described water-soluble alcohol or pure ether compound is 2.0～8.0wt%, and most preferred content is 3.0～5.0wt%.
Described non-ionic surfactant does not have the special construction requirement, and well-known all kinds of non-ionic surfactants all can be realized purpose of the present invention, preferably has at least a in the APES base polymer of following structural formula:
R in the formula
1Be selected from H
+, carbon number 1～12 alkyl, aryl, aralkyl or halogen radical, R
2Be selected from H
+, the alkyl of carbon number 1～12, aryl, polymerization degree n between 6～25, most preferably NPE NP-10, NP-16 and OPEO OP-10 or their composition.
The preferred content of described non-ionic surfactant is 0.05～1.0wt%, and most preferred content is 0.1～0.5wt%.
The neutral developer solution of positive light-sensitive polyimides photoresist provided by the invention, utilize this discovery of dissolubility difference in the different content amide aqueous solution of polyimide and presoma photosensitive resin thereof dexterously, adopt 30.0～60.0wt% water-soluble amide compounds to cooperate with water, the exposure area of positive light-sensitive polyimides photoresist and territory, non-exposed area dissolubility contrast therein is huge, exposed portion can quick and complete dissolving and unexposed portion dissolves hardly, therefore has good developing performance; The perviousness of non-ionic surfactant makes to develop carries out very fully; Water-soluble alcohol or pure ether compound have stably dispersing, froth breaking and hydrotropy effect concurrently, make developer solution have good dispersion stabilization and defoaming.
It is neutral that developer solution provided by the invention is, and the pH value is about 6.5～7.5, uses when being particularly suitable for that on the substrate of alkali sensitivity or functional membrane the positive light-sensitive polyimides photoresist carried out photoetching.
(thickness does not have special restriction with spin-coating legal system film with the positive light-sensitive polyimides photoresist, better with 0.5～10 μ m effect), 105 ℃ of preliminary drying 120s, ultraviolet photoetching, then with positive light-sensitive polyimides photoresist provided by the invention with neutral developer solution with spray mode develop 90s, pure water rinsing, hot blast drying and 350 ℃ of imidizations 1～2 hour, can obtain litho pattern.Gained pattern line acumen, clear picture.
Embodiment
Following examples be to positive light-sensitive polyimides photoresist of the present invention with the further specifying of neutral developer solution, rather than limit the scope of the invention.
Embodiment 1:
In the clean beaker of 250ml, take by weighing N successively, the deionized water 55.7g of N dimethyl formamide 40.0g, absolute ethyl alcohol 4.0g, NPE (NP-10) 0.3g, pH=7.0, stir and promptly get developer solution of the present invention, the pH value is about 7.1, and development effect is as shown in table 1.
Embodiment 2～6:
Basic step is with embodiment 1, and difference is to form and the content difference.Concrete composition, content and development effect are as shown in table 1.
Comparative example 1～3:
Comparative example is used to illustrate developer solution of the prior art.Basic step is with embodiment 1, and difference is to form and the content difference.Concrete composition, content and development effect are as shown in table 1.
The evaluation of development effect:
The litho pattern that obtains after developing is observed the exposure area down in 1000 power microscopes noresidue, presses following standard evaluation:
Zero: noresidue; △: small amount of residual thing; ●: a large amount of residues.
Table 1 developer solution is formed and development effect
Claims (7)
1. the neutral developer solution of positive light-sensitive polyimides photoresist, its component comprises the water-soluble amide compounds of 30.0～60.0wt%, water-soluble alcohol or pure ether compound, the non-ionic surfactant of 0.01～3.0wt% and the water of surplus of 1.0～10.0wt%, and its pH value is between 6.5～7.5.
2. the neutral developer solution of positive light-sensitive polyimides photoresist according to claim 1, it is characterized in that, described water-soluble amide compounds is formamide, acetamide, propionamide, butyramide, isobutyramide, N, dinethylformamide, N, N-diethylformamide, N, N-dimethyl acetamide, N, N-diethyl acetamide, N-Methyl pyrrolidone, N-ethyl pyrrolidone or their composition.
3. the neutral developer solution of positive light-sensitive polyimides photoresist according to claim 1 is characterized in that the content of described water-soluble amide compounds is 35.0～55.0wt%.
4. the neutral developer solution of positive light-sensitive polyimides photoresist according to claim 1, it is characterized in that described water-soluble alcohol or pure ether compound are methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or their composition.
5. the neutral developer solution of positive light-sensitive polyimides photoresist according to claim 1 is characterized in that the content of described water-soluble alcohol or pure ether compound is 2.0～8.0wt%.
6. the neutral developer solution of positive light-sensitive polyimides photoresist according to claim 1 is characterized in that, described non-ionic surfactant is to have at least a in the APES base polymer of following structural formula:
R in the formula
1Be selected from H
+, carbon number 1～12 alkyl, aryl, aralkyl or halogen radical, R
2Be selected from H
+, the alkyl of carbon number 1～12, aryl, polymerization degree n is between 6～25.
7. the neutral developer solution of positive light-sensitive polyimides photoresist according to claim 1 is characterized in that the content of described non-ionic surfactant is 0.05～1.0wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100460781A CN101364055B (en) | 2008-09-17 | 2008-09-17 | Neutral developer solution for positive light-sensitive polyimides photo resist |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100460781A CN101364055B (en) | 2008-09-17 | 2008-09-17 | Neutral developer solution for positive light-sensitive polyimides photo resist |
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| Publication Number | Publication Date |
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| CN101364055A CN101364055A (en) | 2009-02-11 |
| CN101364055B true CN101364055B (en) | 2011-11-09 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8900802B2 (en) * | 2013-02-23 | 2014-12-02 | International Business Machines Corporation | Positive tone organic solvent developed chemically amplified resist |
| CN103955119A (en) * | 2014-04-17 | 2014-07-30 | 富士胶片电子材料（苏州）有限公司 | Developing solution in semiconductor integrated circuit |
| CN103955122A (en) * | 2014-05-06 | 2014-07-30 | 富士胶片电子材料（苏州）有限公司 | Developing solution for color filter |
| CN103955121A (en) * | 2014-05-06 | 2014-07-30 | 富士胶片电子材料（苏州）有限公司 | Developing solution for color filter |
| CN107678252A (en) * | 2017-09-19 | 2018-02-09 | 合肥惠科金扬科技有限公司 | One kind is used for AMOLED negative photo glue developing solutions |
| WO2024124547A1 (en) * | 2022-12-16 | 2024-06-20 | Dow Global Technologies Llc | Solvent composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001228630A (en) * | 2000-02-16 | 2001-08-24 | Fuji Photo Film Co Ltd | Developing solution for developing photosensitive resin, image forming method, method for producing color filter, method for producing active matrix substrate with color filter and liquid crystal display |
| JP2004117981A (en) * | 2002-09-27 | 2004-04-15 | Fuji Photo Film Co Ltd | Developing solution for photosensitive planographic printing plate |
| JP2004184648A (en) * | 2002-12-03 | 2004-07-02 | Clariant (Japan) Kk | Rinse liquid for lithography, and method for resist pattern formation using same |
| CN1916772A (en) * | 2005-07-28 | 2007-02-21 | 罗门哈斯电子材料有限公司 | Stripper |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001228630A (en) * | 2000-02-16 | 2001-08-24 | Fuji Photo Film Co Ltd | Developing solution for developing photosensitive resin, image forming method, method for producing color filter, method for producing active matrix substrate with color filter and liquid crystal display |
| JP2004117981A (en) * | 2002-09-27 | 2004-04-15 | Fuji Photo Film Co Ltd | Developing solution for photosensitive planographic printing plate |
| JP2004184648A (en) * | 2002-12-03 | 2004-07-02 | Clariant (Japan) Kk | Rinse liquid for lithography, and method for resist pattern formation using same |
| CN1916772A (en) * | 2005-07-28 | 2007-02-21 | 罗门哈斯电子材料有限公司 | Stripper |
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