CN111562728B - Developer composition for flat panel display and semiconductor field - Google Patents
Developer composition for flat panel display and semiconductor field Download PDFInfo
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- CN111562728B CN111562728B CN202010490266.4A CN202010490266A CN111562728B CN 111562728 B CN111562728 B CN 111562728B CN 202010490266 A CN202010490266 A CN 202010490266A CN 111562728 B CN111562728 B CN 111562728B
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- nonionic surfactant
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
Abstract
The invention belongs to the technical field of surfactants, and particularly relates to a chemical preparation used in the field of flat panel display and semiconductors, which is used for developing photoresist in developers in the field of flat panel display and semiconductors. Comprises 10-30% of specific Gemini type polyether nonionic surfactant with different EO values, 5-20% of alkaline substance and 50-80% of high-purity water. According to the invention, through the blending of two different EO values of the specific Gemini type nonionic surfactant, the dosage of the surfactant in the developing solution can be obviously reduced, the concentration of the developing solution stock solution is obviously improved, the developing performance is effectively improved, the developing speed of the developing solution is moderate, the pattern is clear, the edge is complete, no photoresist residue is left, the developing solution is stable in dispersion on the developing residue, the foam is small, the cost is low, and meanwhile, the transportation pressure and the cost of the high-concentration developing solution are greatly reduced.
Description
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to a developer composition used in the field of flat panel display and semiconductors, which is used for developing negative photoresist in the flat panel display and semiconductors.
Technical Field
In the manufacturing process of flat panel display and semiconductor fields, a plurality of processes are involved, wherein a part of the processes involve developing solutions of negative photoresist. The photolithography process for fabricating devices in the flat panel display and semiconductor fields generally includes glue application, pre-baking, exposure, development, post-baking, etc. to obtain corresponding devices. And removing the photoresist solvent in the pre-baking process, carrying out exposure selection on different areas through a mask plate, removing an exposed area through alkaline developing solution, and leaving an unexposed area to obtain a corresponding pattern. Common development methods include immersion development, shaking development, spray development, and standing development.
The developing solution usually adopts organic or inorganic alkaline substances as main components for dissolving the photoresist, but a solution consisting of pure water and alkali is difficult to rapidly and uniformly spread on the surface of the whole photoresist due to overhigh surface tension, so that the defects of uneven development, incomplete development, local insufficient development, excessive development, irregular edge of a developed pattern and the like are caused, and meanwhile, the dissolved photoresist is easy to agglomerate when the concentration of the dissolved photoresist in the developing solution is gradually increased, so that insoluble organic substance residues are formed, adsorbed on a developed photoresist pattern, causing pattern defects and easily blocking a circulating system of a filter element.
The addition of surfactants based on the water + alkali composition is the main solution to the above-mentioned drawbacks. Japanese patent laid-open No. Hei 09-034128 uses a nonionic surfactant of polyoxyethylene ether type as a developer surfactant additive to increase the surface tension of the developer. Patent application publication No. CN109062015A discloses a high-concentration developer stock solution composition, which increases the concentration of the developer stock solution by adding organic amines, organic acids and alcohol ether dissolution aids. Patent application publication No. CN110471262A discloses a developer with a concentration 2-5 times that of the developer in the current market, wherein the developer adopts a gemini type polyether nonionic surfactant, and a certain solubilizer is added to improve the alkali resistance. By adding the auxiliary agent, a plurality of uncertain influencing factors are brought, such as excessive foam, reduced development speed, development residue and the like. The invention adds the surfactant with high alkali resistance degree into the developing solution, the critical micelle concentration is low, the dosage of surface activity is reduced, the concentration of the developing solution stock solution is also improved, the developing is carried out after adding 400 portions of high-purity water of 100 portions of the auxiliary materials, the developing speed of the developing solution is moderate, the graph is clear, the edge is complete, no photoresist residue exists, the developing residue is dispersed and stabilized, the foam is small, the cost is low, and the transportation pressure and the cost of the high-concentration developing solution are greatly reduced.
Disclosure of Invention
The invention mainly solves the technical problem of providing a developer solution composition used in the field of flat panel display and semiconductors, and improves the alkali resistance of the developer solution and simultaneously maintains the developing performance of the developer solution unchanged by adding a specific Gemini type polyether nonionic surfactant.
In order to solve the above problems, the present invention is implemented by the following technical solutions.
A developer composition for flat panel display and semiconductor fields comprises the following components in percentage by mass: 10-30% of specific Gemini polyether nonionic surfactant, 5-20% of alkaline substance and 50-80% of high-purity water. The sum of the total mass fractions is 100%.
The specific Gemini type polyether nonionic surfactant is selected from the following structures:
The specific Gemini polyether nonionic surfactant at least contains one surfactant with n of 6-12 or 12-20.
The alkaline substance is at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide, TMAH (tetramethylammonium hydroxide), tetraethylammonium hydroxide and tetrabutylammonium hydroxide.
The preparation method of the specific Gemini polyether nonionic surfactant comprises the following steps:
the method comprises the following steps: preparation of intermediate 1 with alkyl bridging structure:
1, 5 hexadiene and phenol with twice molar weight are synthesized into an intermediate with an alkyl bridging structure under the action of a catalyst, and the intermediate is shown as a formula 2.
Step two: preparation of intermediate 2 to which the styrene structure is attached:
the intermediate 1 and styrene with twice molar weight are synthesized into an intermediate 2 connected with a styrene structure under the condition of styrene and the action of a catalyst, and the formula is shown as a formula 3.
Step three: preparing a specific Gemini type polyether nonionic surfactant:
under the condition of KOH catalyst, the intermediate 2 reacts with 10-30 times of molar weight of ethylene oxide to generate the specific Gemini type polyether nonionic surfactant.
The invention has the following remarkable advantages:
by adding the specific Gemini type polyether nonionic surfactant and adjusting the mixed addition amount of different EO (ethylene oxide) values, the use amount of the surfactant in the developing solution can be obviously reduced, the concentration of the stock solution of the developing solution is obviously improved, the developing performance is effectively improved, the developing speed of the developing solution is moderate, the graph is clear, the edge is complete, no photoresist residue exists, the developing residue is stably dispersed, the foam is small, the cost is low, and meanwhile, the transportation pressure and the cost of the high-concentration developing solution are greatly reduced. The concentration of the developer is 2-4 times of that of the common developer on the market, and the developer belongs to a high-concentration developer composition.
Drawings
FIG. 1 line edge cross-sectional view after photoresist development
FIG. 2 is a nuclear magnetic spectrum of a specific Gemini polyether nonionic surfactant according to the present invention;
FIG. 3 is a mass spectrum of a specific Gemini polyether nonionic surfactant according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
The preparation method of the specific Gemini type polyether nonionic surfactant comprises the following steps:
the method comprises the following steps: preparation of intermediate 1 with alkyl bridging structure:
1, 5 hexadiene and phenol with twice molar weight are synthesized into an intermediate with an alkyl bridging structure under the action of a 0.5gHY zeolite molecular sieve catalyst, and the intermediate is shown as a formula 2.
Step two: preparation of intermediate 2 to which the styrene structure is attached:
the intermediate 1 and styrene with twice molar weight are synthesized into an intermediate 2 connected with a styrene structure under the condition of styrene and the action of 1ml of concentrated sulfuric acid catalyst, and the formula is shown as a formula 3.
Step three: preparing a specific Gemini type polyether nonionic surfactant:
under the condition of KOH catalyst, the intermediate 2 reacts with 10-30 times of molar weight of ethylene oxide to generate the specific Gemini type polyether nonionic surfactant.
Examples and comparative examples: a developer composition for use in flat panel display and semiconductor applications.
The developer compositions of examples and comparative examples were prepared according to the compositions and mass percentages shown in table 1 below, respectively. Testing the chain length of bridging group alkyl of the Gemini type polyether nonionic surfactant to be m-6, GnThe developer composition is prepared by adding raw materials of different components into Gemini type polyether nonionic surfactants A and B with the addition number of Ethylene Oxide (EO) being n and then uniformly mixing to obtain different embodiments.
TABLE 1
Experimental example: measurement experiment of developing solution developing performance
In order to evaluate the developing performance of the CF developer compositions of examples 1 to 12 and comparative examples 1 to 6 described above, a developer developing performance test was conducted by the following test.
1. Manufacturing test piece
In order to evaluate the developing performance of the developer composition on the photoresist, a 1.5 μm BM negative photoresist or R, G, B photoresist was spin-coated on a 5cm × 5cm glass substrate by the following specific treatments: and thoroughly cleaning the glass substrate by using a special cleaning agent, rinsing by using ultrapure water, and drying by using nitrogen. Spin-coating photoresist on a spin coater at a rotating speed of 300rpm, vacuumizing to remove most of solvent, heating a flat plate at 100 ℃ to cure for 150s, and transferring a mask pattern with a certain line width onto a test piece through an exposure machine to obtain a photoresist test piece with a thickness of about 1.5 mu m for testing the developing performance of the developing solution composition.
2. Development test
Diluting the developing solution composition by 400 times with high-purity water, adjusting the conductivity to 1.1mS/cm, controlling the temperature at 23 ℃, spraying the diluted developing solution on a photoresist test piece at a constant pressure for 60s, rinsing with high-purity water, and drying with nitrogen. Whether the development graph is clear or not is observed under a high-power metallographic microscope, whether burr phenomenon exists at the edge of the graph or not and whether photoresist residue exists or not is observed, whether corrosion exists on a glass substrate or not is judged, and whether insufficient development or excessive development exists or not is observed at the same time. And (4) splitting the developed test piece, and checking the action condition of the developing solution on the photoresist under the microscopic condition, the smoothness degree of the edge of the photoresist and whether the side etching occurs or not under an SEM (scanning electron microscope). The developed developer was filtered through a 0.5 μm filter and observed for clogging. The results are shown in Table 2.
TABLE 2
As can be seen from Table 1, when the EO value of the polyether in comparative example 1 is 8, the developing solution is milky turbid in the formulation of a high concentration developer, and the development test cannot be carried out, as compared with the examples. Comparative example 2, the EO value is increased to 11, the developing performance of the developer is better, but the cloud point is too low, and the preparation requirement of the developer cannot be met. Comparative example 3 further increases the EO value to 13, and the cloud point of the developer is greatly increased, which can substantially meet the formulation requirements, but because the EO value is too large, the performance of the surfactant is reduced, and the developing performance begins to be deficient to some extent. Comparative example 4 when the EO value was increased to 18, the cloud point of the developer was high, but the developing property was poor and could not satisfy the requirements. Comparative examples 1-4 show that the developer with only a single EO surfactant can not meet the developer requirements, and that a developer with good performance can only be obtained by combining gemini polyether surfactants with different EO values.
Compared with the comparative examples 5 and 6, two common nonionic surfactants TX-10 and an anionic surfactant AES are adopted, so that the alkali resistance of the nonionic surfactant TX-10 is poor, the developing solution performance reaches a common level, the alkali resistance of the anionic surfactant AES is excellent, the anionic surfactant can bear high alkali content, but the developing performance is poor, and the foams of the two surfactants are extremely high, so that the spraying condition of the developing solution cannot be met. In conclusion, the positive progress effects of the invention are as follows: by adding the specific Gemini type polyether nonionic surfactant and adjusting the mixed addition amount of different EO values, the use amount of the surfactant in the developing solution can be obviously reduced, the concentration of the developing solution stock solution is obviously improved, the developing performance is effectively improved, the developing speed of the developing solution is moderate, the pattern is clear, the edge is complete, no photoresist residue exists, the developing residue is dispersed and stabilized, the foam is small, the cost is low, and meanwhile, the transportation pressure and the cost of the high-concentration developing solution are greatly reduced.
FIG. 1 is a cross-sectional view of a line edge after photoresist development; FIG. 2 is a nuclear magnetic spectrum of a specific Gemini type polyether nonionic surfactant with m being 6 and n being 12 according to the invention;1HNMR(400MHz,DMSO-d6) δ 7.26-7.00 (m,32H), 5.76-5.67 (m,2H),4.59(d, J ═ 5.8Hz,4H),4.04(d, J ═ 4.8Hz,4H),3.72(dt, J ═ 14.4,7.4Hz,8H),3.52(d, J ═ 6.7Hz,102H), 1.72-1.32 (m, 18H); fig. 3 is a mass spectrum diagram of the specific Gemini type polyether nonionic surfactant with m being 6 and n being 12.
The above embodiments describe the present invention in detail, but they are only examples and do not limit the scope of the invention. All equivalent modifications and substitutions made by the present specification are within the scope of the present invention and are included in the patent protection scope of the present invention.
Claims (3)
1. A developer composition for flat panel display and semiconductor fields is characterized by comprising the following components in percentage by mass: 10-30% of specific Gemini type polyether nonionic surfactant, 5-20% of alkaline substance and 50-80% of high-purity water, wherein the sum of the total mass fraction is 100%; the specific Gemini type polyether nonionic surfactant is selected from the following structures:
2. The composition of claim 1, wherein the alkaline material is at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide, TMAH, TETHAH, and tetrabutylammonium hydroxide.
3. The developer composition according to claim 1, wherein the specific Gemini polyether nonionic surfactant is prepared by the following steps:
the method comprises the following steps: preparation of intermediate 1 with alkyl bridging structure:
1, 5 hexadiene and phenol with twice molar weight are synthesized into an intermediate 1 with an alkyl bridging structure under the action of 0.5g HY zeolite molecular sieve catalyst, and the intermediate is shown as a formula 2:
formula 2;
step two: preparation of intermediate 2 to which the styrene structure is attached:
intermediate 1 with twice the molar amount of styrene in styreneAn intermediate 2 connected with a styrene structure is synthesized under the alkene condition and the action of 1ml of concentrated sulfuric acid catalyst, and is shown as a formula 3:
formula 3;
step three: preparing a specific Gemini type polyether nonionic surfactant:
under the condition of KOH catalyst, the intermediate 2 reacts with 10-30 times of molar weight of ethylene oxide to generate the specific Gemini type polyether nonionic surfactant.
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| CN101178548B (en) * | 2006-11-08 | 2011-08-10 | 新应材股份有限公司 | Alkaline-based developer composition |
| JP2009237169A (en) * | 2008-03-26 | 2009-10-15 | Fujifilm Corp | Method of making planographic printing plate |
| JP5052450B2 (en) * | 2008-07-30 | 2012-10-17 | 富士フイルム株式会社 | Alkali developer for colored photosensitive composition, image forming method, color filter, and liquid crystal display device |
| CN107219731A (en) * | 2017-05-11 | 2017-09-29 | 苏州新滤精环保科技有限公司 | A kind of developer composition and preparation method thereof |
| CN110471262A (en) * | 2019-08-28 | 2019-11-19 | 华璞微电子科技(宁波)有限公司 | A kind of colored filter developer composition |
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