WO2016112822A1 - Liquide de développement à base de koh destiné à une photorésine de kmpr - Google Patents

Liquide de développement à base de koh destiné à une photorésine de kmpr Download PDF

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Publication number
WO2016112822A1
WO2016112822A1 PCT/CN2016/070357 CN2016070357W WO2016112822A1 WO 2016112822 A1 WO2016112822 A1 WO 2016112822A1 CN 2016070357 W CN2016070357 W CN 2016070357W WO 2016112822 A1 WO2016112822 A1 WO 2016112822A1
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WIPO (PCT)
Prior art keywords
koh
developer
hpo
kmpr
development
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PCT/CN2016/070357
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English (en)
Chinese (zh)
Inventor
周国富
李发宏
窦盈莹
水玲玲
海耶斯罗伯特·安德鲁
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深圳市国华光电研究院
华南师范大学
深圳市国华光电科技有限公司
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Application filed by 深圳市国华光电研究院, 华南师范大学, 深圳市国华光电科技有限公司 filed Critical 深圳市国华光电研究院
Publication of WO2016112822A1 publication Critical patent/WO2016112822A1/fr

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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

Definitions

  • the present invention relates to a developer for a photoresist, and more particularly to a KOH developer which can develop a KMPR paste.
  • the pixel wall surrounds the smallest display unit, which is an important component of the display, and the fabrication of the pixel wall is usually obtained by photolithography using a photolithography process.
  • the photoetching agent is a photosensitive resin composition, which is divided into two types: positive and negative, the exposed area is developed, and the unexposed area cannot be developed as a positive photoresist, and vice versa.
  • Photo etchant Taking a negative photoresist as an example, first, a photoresist is coated on the substrate, the photoresist is pre-baked, and then exposed to light by a mask, and then washed with a developer.
  • the photoetching agent in the unexposed area covered by the mask can leave a desired photoresist pattern according to the pattern of the mask, specifically a matrix pattern, and each matrix point corresponds to each pixel.
  • Conventionally used development methods include immersion development, shaking development, spray development, and puddle, and the developer includes an organic solvent, an alkaline developer, and the like.
  • an alkaline developing solution is often used.
  • the commonly used alkaline developing solution is a salt solution of various alkali liquids and alkali metals such as KOH aqueous solution, NaOH aqueous solution, TMAH aqueous solution.
  • MicroChem's KMPR photoresist is an excellent photoresist material for the preparation of pixel walls. Through the choice of viscosity, we can obtain pixel walls of different heights, and And KMPR photoresist is more hydrophilic than the commonly used SU8 photoresist, and is more suitable for electrowetting display technology and its industrialization.
  • the developer of KMPR glue recommended by MicroChem is an organic solvent (such as PGMEA) or 2.38wt% TMAH solution.
  • the organic solvent developer is not suitable for industrial production due to its environmental problems, and the TMAH solution takes a long time to develop KMPR. The development effect is far less than that of its organic solvent developer, so the industrial use of KMPR glue is affected.
  • the technical problem to be solved by the present invention is to provide a KOH developing solution for KMPR glue, which can avoid the environmental protection problem caused by the use of the organic solvent developing solution, and has a short development time and is suitable for industrial production.
  • the solution to the technical problem of the present invention is: a KOH developer for KMPR photoresist, which consists of KOH and deionized water, wherein the KOH content is from 0.01 to 10% by weight.
  • the development mechanism of the alkaline developing solution is: first, OH - enters the macromolecular film void, chemically reacts with the acidic group of the photoresist substance, and then the cation ( K + ) reaches the reaction interface for charge neutralization. Theoretically, after these steps, a reaction product is carried away from the developer-photoresist film reaction interface into the KOH developer body.
  • the developing temperature is also an important factor affecting the development speed.
  • the development mechanism of KOH developer is: first, OH - enters the macromolecular film void, chemically reacts with the photoresist material, and then the cation (K + ) reaches the reaction interface for charge neutralization. . Therefore, the development process is actually a chemical reaction process.
  • the chemical reaction rate is increased by 4 to 6 times for the development process, as shown in FIG. 2 .
  • the 0.4 wt% KOH developer exhibited a spot time of 190 s at 22 ° C and a spot time of 45 s at 32 ° C.
  • the developing temperature is generally controlled at 22 to 40 ° C. Therefore, in combination with the influence of temperature and concentration on the developing speed, the KOH concentration of the developing solution in the embodiment of the present invention is 0.01 to 10% by weight.
  • KOH showed a concentration of 0.4 wt% and 0.1 wt%.
  • the liquid solution can reach the display time of ⁇ 60s between 30-40 °C, and the display time of 30-60s is an ideal time range in actual production or scientific research process, although high concentration can also be realized.
  • the development time is lowered, but the excessive concentration causes excessive KOH consumption, which is disadvantageous to environmental protection. Therefore, the preferred concentration of KOH is in the range of 0.1 to 1% by weight, and in actual use, the temperature adjustment can be combined to shorten the display time.
  • the above-mentioned development time is taken as a negative gel as an example of the time required for the unexposed dry film to be dissolved from the substrate.
  • a development time is generally added on the basis of the display time, which is called the actual development time.
  • the developer further includes a buffering agent such as a phosphate, a carbonate, a borate, an amine salt, etc.
  • a buffering agent such as a phosphate, a carbonate, a borate, an amine salt, etc.
  • the buffer of the invention uses potassium salt K 2 HPO 4 , and the amount of K 2 HPO 4 added is determined according to the following steps:
  • the combined actual process refers specifically to the ratio of the molar concentration of KOH and K 2 HPO 4 in the developing solution obtained in step 2), the concentration of KOH is selected according to the process requirements, and then the amount of K 2 HPO 4 is calculated. .
  • the KOH concentration and temperature of the KOH developer in the step 1) are selected according to the development time, and the concentration ranges from 0.1 to 1% by weight, and the temperature ranges from 22 to 40 °C.
  • the developer further includes a surfactant, and the surfactant is a Tween, a Span or a polyoxyethylene ether.
  • the surfactant is a Tween, a Span or a polyoxyethylene ether.
  • nonionic surfactants such as Span20, Span60, Span80, Tween20, Tween40, Tween60, Tween80, AEO3, AEO7, AEO9, etc.
  • anionic surfactants such as SDS (sodium dodecyl sulfate), dodecane Sodium sulfonate and the like.
  • the surfactant is contained in an amount of from 0.001 to 1% by weight, further, from 0.005 to 0.5% by weight.
  • the developer further includes 0.1 to 1% by weight of an antifoaming agent.
  • the antifoaming agent may be a silicone-based antifoaming agent, a surfactant-based antifoaming agent, or the like, such as a silicone polyether defoaming agent, a non-silicone polyether defoaming agent, or the like.
  • the antifoaming agent is present in an amount of from 0.2 to 0.7% by weight.
  • the invention has the beneficial effects that the present invention can develop KMPR glue by exploring a suitable concentration of KOH solution, and further, adding K 2 HPO 4 to the KOH developing solution to prepare an alkaline buffer solution, with the alkaline in the developing solution.
  • the group is gradually neutralized, which promotes the hydration reaction of the buffer solution material, thereby releasing the basic group, reducing the speed at which the developer development efficiency is weakened, and the sustained release effect of the basic group is delayed, thereby delaying the production.
  • the adjustment of the development time improves the quality and stability of the product.
  • a surfactant, an antifoaming agent or the like may be added to the developing solution.
  • the KMPR paste KOH developer of the present invention can better develop KMPR glue without polluting the environment like an organic solution.
  • Figure 1 is a development time of different concentrations of KOH developer of the present invention
  • Figure 2 is the effect of temperature on the development time of the KOH developer
  • FIG. 3 is a graph showing a development effect of a pixel wall according to an embodiment of the present invention.
  • Figure 4 is a comparison of the development efficiency of the KOH developer of Example 3 of the present invention with the KOH-K 2 HPO 4 buffer developer of Example 7.
  • KMPR photoresist is a photoresist-based material available for the pixel wall of the electrowetting process other than SU8.
  • KMPR series photoresists can achieve pixel wall heights of 2-50 ⁇ m, meeting the requirements of electrowetting process.
  • KMPR 1005 can coat 4-10 ⁇ m high pixel walls.
  • Example 1 Weigh a certain amount of KOH, dissolve it in 100 mL of deionized water, shake it evenly, and obtain a developing solution having a concentration of 0.1% by weight, and add the obtained developing solution to the developing tank. Under the condition of 24 ° C, the 3-inch substrate (side length 7.6 cm) was developed, and the height of the pixel wall formed by the photoresist KMPR on the substrate was 6-7 ⁇ m, and the development method was: shaking development.
  • Example 2 Development at 35 ° C, the same conditions as in Example 1.
  • Example 3 Weigh a certain amount of KOH, dissolve it in 100 mL of deionized water, shake it evenly, and obtain a developing solution with a concentration of 0.4 wt%. Add the obtained developing solution to the developing tank, and develop 3 inches at 24 ° C.
  • the substrate side length 7.6 cm
  • the pixel wall formed by the photoresist KMPR on the substrate has a height of 6-7 ⁇ m
  • the development method is: shaking development.
  • Example 4 Development at 26 ° C, the same conditions as in Example 3.
  • Example 5 Development at 32 ° C, the same conditions as in Example 3.
  • Example 6 Weigh a certain amount of KOH, dissolve it in 100 mL of deionized water, shake it evenly to obtain a developing solution having a concentration of 2 wt%, add the obtained developing solution to a developing tank, and develop a 3-inch substrate at 24 ° C. (side length 7.6 cm), the pixel wall formed by the photoresist KMPR on the substrate has a height of 6-7 ⁇ m, and the development method is: shaking development.
  • Example 7 Weigh a certain amount of KOH, dissolve it in 100 mL of deionized water, shake it evenly to obtain a KOH solution having a concentration of 0.4 wt%, and further, add K 2 HPO 4 to prepare a KOH-K 2 HPO 4 buffer developed
  • the amount of K 2 HPO 4 added is calculated according to the following steps:
  • the obtained KOH-K 2 HPO 4 buffer developing solution was set to have the same pH as the 0.4 wt% KOH developing solution.
  • the prepared KOH-K 2 HPO 4 buffer developing solution was added to the developing cell, and the 3 inch substrate (side length 7.6 cm) was developed at 24 ° C, and the pixel wall height of the photoresist KMPR on the substrate was 6-7 ⁇ m.
  • development method shaking and developing.
  • Example 8 Development at 26 ° C, the same conditions as in Example 7.
  • Example 9 0.012% by weight of Tween 20 was added to the developing solution, and the remaining conditions were the same as in Example 4.
  • Example 10 0.012% by weight of Span 80 was added to the developing solution, and the other conditions were the same as in Example 4.
  • Example 11 0.006 wt% of Span 80 and 0.006 wt% of Tween 20 were added to the developer, the same conditions as in Example 4.
  • Example 12 0.006 wt% of Span 80 and 0.006 wt% of SDS (sodium dodecyl sulfate) were added to the developer, and the same conditions were the same as those in Example 4.
  • SDS sodium dodecyl sulfate
  • Example 13 0.012 wt% of Span 80 was added to the developer, and the rest of the conditions were the same as in Example 8.
  • the developing solution commonly used for KMPR adhesives includes the organic solvent PGMEA developer and TMAH developer, so the two developers are selected for comparison with the KOH developer of the present invention.
  • Comparative Example 1 100 mL of PGMEA organic solvent developer was added to a developing cell at Under the condition of 24 ° C, the 3 inch substrate (side length 7.6 cm) was developed, and the height of the pixel wall formed by the photoresist KMPR on the substrate was 6-7 ⁇ m, and the development method was: shaking development.
  • Comparative Example 2 100 mL of a 2.38 wt% TMAH developer was added to a developing cell, and a 3 inch substrate (side length 7.6 cm) was developed at 24 ° C.
  • the pixel wall height of the photoresist KMPR on the substrate was 6 -7 ⁇ m, development method: shaking development.
  • the development time of the developer in the above Examples 1-13 and Comparative Example 1-2 was measured, and the preferred embodiment was used to fix the actual development time, and the measurement was performed using a step meter to plot the development curve of the pixel wall.
  • the test results are shown in the table. 1.
  • Example 3 shows that there is no difference in the time for developing the first substrate under the same conditions for both the KOH developer and the KOH-K 2 HPO 4 buffer developer, but further development is carried out by testing different numbers of sheets.
  • the conductivity of the liquid shows that the conductivity of the KOH developer is slower than that of the KOH-K 2 HPO 4 buffer developer under the condition that the initial developer pH and the developer volume are the same, that is, The addition of K 2 HPO 4 serves as a buffering effect, and the developing efficiency of the developing solution is lowered, so that the number of developing portions of the developing solution can be increased.
  • the concentration of KOH in the selected KOH-K 2 HPO 4 buffer developing solution is the same as the concentration of KOH in the corresponding KOH developing solution, but in practical application, those skilled in the art can, as needed, Different KOH concentrations were selected, and the concentration of K 2 HPO 4 was calculated according to the formula provided, and the amount of addition was determined.
  • Examples 9-13 show preferred embodiments of a developer having a surfactant.
  • the addition of the surfactant under the same conditions.
  • the development time of the developer is not significant influences.
  • the addition of the surfactant is advantageous for improving the surface of the photoresist. Wettability. It is indicated that the addition of the surfactant is mainly to improve the wettability of the surface of the photoresist, and there is no significant improvement in the time of the display.
  • the preferred embodiment is a KOH developing solution in which 0.012% by weight of Span 80 is added, and the contact angle of water droplets in the unexposed area, the exposed area, and the mixed area of the two is lowered by 10°, 19°, and 15°, respectively. That is, the addition of the surfactant in the KOH developer improves the wettability of the surface of the KMPR gel, which facilitates uniform development. Also, as shown in Example 2 and Example 13 of Table 2, for the buffer developing solution of KOH-K 2 HPO 4 , the addition of the surfactant causes the contact angle of the buffer developing solution on the surface of the KMPR gel to be lowered, and the surface wettability is enhanced. .
  • the developer of the present invention may further comprise 0.1 to 1% by weight of an antifoaming agent.
  • the antifoaming agent may be a silicone-based antifoaming agent, a surfactant-based antifoaming agent, or the like, such as a silicone polyether defoaming agent, a non-silicone polyether defoaming agent, or the like.
  • the content of the antifoaming agent is 0.2-0.7 wt%, and the amount and type of defoaming agent added are selected by those skilled in the art as needed, and will not be described herein.
  • composition and effect of the developer of the present invention have been described by taking shaking development as an example, but the developer of the present invention is not only suitable for the development method, but also suitable for various other development methods, including spray development, Let stand for development and the like.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

L'invention concerne un liquide de développement à base de KOH destiné à une photorésine de KMPR. Le liquide de développement comprend une quantité appropriée de KOH et d'eau déionisée. En outre, du K2HPO4 est ajouté dans le liquide de développement à base de KOH pour préparer une solution tampon, une réaction d'hydratation des substances dans la solution tampon est favorisée avec la neutralisation progressive des groupements basiques contenus dans le liquide de développement, de manière à libérer des groupements basiques supplémentaires, de manière à réduire la vitesse de réduction de l'effet de développement du liquide de développement, et de manière à obtenir un effet de libération prolongée des groupements basiques, ce qui permet de repousser l'ajustement d'un temps de développement pendant la production, et d'améliorer la qualité et la stabilité d'un produit. En outre, afin d'obtenir un meilleur effet de développement, un tensioactif, un agent anti-mousse et similaires peuvent également être ajoutés dans le liquide de développement. Le liquide de développement à base de KOH destiné à la photorésine de KMPR peut mieux développer la photorésine de KMPR, sans provoquer de pollution de l'environnement comme une solution organique.
PCT/CN2016/070357 2015-01-14 2016-01-07 Liquide de développement à base de koh destiné à une photorésine de kmpr WO2016112822A1 (fr)

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CN201510018447.6A CN104597727A (zh) 2015-01-14 2015-01-14 一种kmpr光刻胶用koh显影液
CN201510018447.6 2015-01-14

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Publication number Priority date Publication date Assignee Title
CN104597727A (zh) * 2015-01-14 2015-05-06 深圳市国华光电科技有限公司 一种kmpr光刻胶用koh显影液
CN105589303A (zh) * 2015-12-23 2016-05-18 苏州瑞红电子化学品有限公司 一种用于厚膜光刻胶的高容量显影液组合物
CN105589304B (zh) * 2016-03-04 2020-08-14 苏州晶瑞化学股份有限公司 一种光刻胶用显影液及其制备方法和应用
CN108170010A (zh) * 2017-12-29 2018-06-15 苏州碳方新材料科技有限公司 一种环保显影液
CN110727180A (zh) * 2018-07-17 2020-01-24 南昌欧菲显示科技有限公司 一种自净化型显影液组合物及其制备方法及使用其的显影方法
CN114284396B (zh) * 2021-12-24 2023-08-22 苏州大学 栅线电极制备方法及太阳能电池

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US4822722A (en) * 1985-07-18 1989-04-18 Petrarch Systems, Inc. Process of using high contrast photoresist developer with enhanced sensitivity to form positive resist image
US20040096777A1 (en) * 2000-07-14 2004-05-20 Fuji Photo Film Co., Ltd. Developing solution for photosensitive lithographic printing plate, plate-making method of lithographic printing plate, and photosensitive lithographic printing plate
CN101641647A (zh) * 2007-01-17 2010-02-03 索尼株式会社 显影液以及制备微细加工材料的方法
CN101999097A (zh) * 2008-07-29 2011-03-30 东亚合成株式会社 导电性高分子的图案形成方法
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