Developer and Developing Process for High Selectivity of Alkaline-Soluble Photoresist

Abstract

The present invention relates to the field of developing technology, specifically to a developer and a developing process with high selectivity for alkali-soluble photoresist. The present invention overcomes the problems of poor developing effect and dissolution effect existing in the developing process. The synthetic raw materials of the developer in the present invention include a modified active agent, a weak alkaline mixture, a modified defoaming agent, a composite dispersant, an improved chelating agent, an organic solvent, and deionized water. The present invention improves the dissolution rate of the unexposed photoresist by preparing the modified active agent and the weak alkaline mixture, reflecting the high selectivity of the developer; improves the defoaming performance of the developer by preparing the modified defoaming agent and adding the composite dispersant; the improved chelating agent in the developer and the organic solvent act synergistically to improve the developing effect of the material; applying the developer to the developing process, adjusting the pH value and process parameters, so as to improve the developing effect and efficiency of the material.

Description

Technical Field

[0001] The present invention relates to the technical field of development, and specifically to a developer and a developing process for high selectivity of alkali-soluble photoresist. Background Art

[0002] Alkali-soluble negative photoresist is composed of a pigment dispersion, a solvent, a photosensitive resin, and related additives. Short-chain molecules containing polymers will crosslink into long-chain molecules due to light exposure. Generally, first, a certain thickness of photoresist is formed on a glass substrate or a base material by coating. After exposure, a developer is used for development to remove the unexposed part of the photoresist, thereby obtaining the required image. During this process, the alkali-soluble negative photoresist will solidify in the exposed area, and the unexposed area will maintain its original form and is easily removed in the developer at this time. Generally speaking, the alkali-soluble negative photoresist is acidic, even after solidification. Therefore, if the developing process is not specially designed, it will affect the solidified part.

[0003] Currently, spray-type developing equipment is basically used in the developing process. By controlling the running speed of the equipment, the length of the developing time is controlled. After the developing section is completed, a post-rinse process is carried out to thoroughly rinse the residual developer and photoresist to ensure the developing quality of the product. The macromolecular photoresist particles after the reaction between the developer and the photoresist are hydrophobic. If the solubility of the developer is poor, it will cause the photoresist particles to agglomerate, resulting in abnormalities and even clogging the filter element in severe cases. Due to the small chemical difference between the uncured and cured forms of the alkali-soluble negative photoresist, the developing process is likely to cause some of the solidified photoresist to be removed or pinhole phenomena to occur.

[0004] Therefore, there are still problems with poor developing effect and dissolving effect in the current developing process, which limits its development in the field of development.

[0005] For this reason, a developer and a developing process for high selectivity of alkali-soluble photoresist are proposed. Summary of the Invention

[0006] The purpose of the present invention is to design a developer and a developing process for high selectivity of alkali-soluble photoresist. The synthetic raw materials of the developer in the present invention include a modified surfactant, a weak alkaline mixture, a modified defoamer, a composite dispersant, a modified chelating agent, an organic solvent, and deionized water. The present invention improves the dissolution rate of the unexposed photoresist by preparing a modified surfactant and a weak alkaline mixture, reflecting the high selectivity of the developer; improves the defoaming performance of the developer by preparing a modified defoamer and adding a composite dispersant; the modified chelating agent in the developer and the organic solvent act synergistically to improve the developing effect of the material; applying the developer to the developing process and adjusting the pH value and process parameters, thereby improving the developing effect and efficiency of the material.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] On the one hand, the present invention provides a developer for an alkali-soluble photoresist. In terms of mass percentage, the synthesis raw materials of the developer include the following components:

[0009] Modified active agent: 8% - 12%;

[0010] Weak alkaline mixture: 5% - 7%;

[0011] Modified defoaming agent: 3% - 5%;

[0012] Compound dispersant: 1% - 3%;

[0013] Modified chelating agent: 1% - 3%;

[0014] Organic solvent: 9% - 15%;

[0015] Deionized water: the balance; the total mass percentage is 100%.

[0016] Preferably, the preparation method of the modified active agent is as follows: Put 8 parts of sodium dodecylbenzenesulfonate and 3 parts of ferrous sulfate into a mixed solution of methanol and deionized water, and stir for 30 minutes to obtain a mixed solution A; add 2 parts of hydrogen peroxide to the mixed solution A, control the stirring temperature at 50°C - 90°C, and the stirring time at 3h - 5h. After the reaction, centrifuge at a speed of 5000 rpm, and vacuum-dry the centrifuged solid at 60°C for 12h to obtain the modified active agent; the weight ratio of methanol to deionized water is 1:2.

[0017] Preferably, the weak alkaline mixture is a mixture of sodium dihydrogen phosphate, sodium metaborate and ethylenediamine, and the weight ratio of sodium dihydrogen phosphate, sodium metaborate and ethylenediamine is 3 - 5:2:1.

[0018] Preferably, the preparation method of the modified defoaming agent is as follows: Put 6 parts of polydimethylsiloxane and 5 parts of fatty alcohol polyoxyethylene ether into 15 parts of toluene, stir for 20 minutes until completely dissolved to obtain a solution A; add 3 parts of benzoyl peroxide to the solution A, stir for 1h, then transfer it to a hydrothermal reaction kettle, and react at 85°C - 105°C for 5h - 7h. After the reaction is completed, obtain the modified defoaming agent through centrifugal drying.

[0019] Preferably, the compound dispersant is a mixture of polyvinylpyrrolidone, sodium polyacrylate and cetyltrimethylammonium bromide, and the weight ratio of polyvinylpyrrolidone, sodium polyacrylate and cetyltrimethylammonium bromide is 1 - 2:1:1 - 2.

[0020] Preferably, the preparation method of the modified chelating agent is as follows: Dissolve 10 parts of disodium ethylenediaminetetraacetate and 5 parts of diethylenetriaminepentaacetic acid in 20 parts of deionized water, and stir for 25 min to obtain a mixed solution A; Dissolve 3 parts of diethylenetriamine in 5 parts of deionized water, and stir for 15 min to obtain a mixed solution B; Under stirring conditions, slowly drop the mixed solution B into the mixed solution A, adjust the pH value of the reaction system to 8 with sodium hydroxide solution, and stir and react at a temperature of 60 °C - 80 °C for 7 h - 9 h. After the reaction is completed, centrifuge and dry to obtain the modified chelating agent.

[0021] Preferably, the organic solvent is one or two of methanol, ethanol, and N,N-dimethylformamide; the resistivity of the deionized water is not less than 18 MΩ.

[0022] Preferably, the developer is obtained by mixing the above materials by mass percentage.

[0023] On the other hand, the present invention provides a developing process for an alkali-soluble photoresist. Apply the above developer to the developing process, and the specific steps are as follows:

[0024] S1 Prepare the developer well, place it in a constant-temperature storage container, and adjust the temperature of the developer to 10 °C - 15 °C; Place the exposed sample steadily on the operating table, set the spraying pressure to 60 kPa - 80 kPa, the spraying angle to 80°, and the moving speed of the nozzle to 130 mm / s - 170 mm / s. After spraying, a semi-developed sample is obtained;

[0025] S2 After development is completed, immediately rinse the semi-developed sample with deionized water to remove the residual developer and dissolved photoresist on the surface; Then blow dry with nitrogen, and control the nitrogen flow rate at 1.5 L / min to obtain a dried sample; Place the dried sample in an oven and treat it at 80 °C - 100 °C for 1 h to obtain a developed sample.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0027] 1. The present invention improves the solubility of unexposed photoresist and reflects the high selectivity of the developer by preparing a modified active agent and a weak alkaline mixture and changing the mass percentage of the modified active agent. The modified active agent obtained by hydroxylation of sodium dodecylbenzenesulfonate can reduce the interfacial tension between the photoresist and the developer, making it easier for the developer to penetrate into the unexposed photoresist. Its special functional groups can also interact with the photoresist molecules, breaking the intermolecular forces of the photoresist, thereby increasing the dissolution rate of the unexposed photoresist in the developer; the weak alkaline mixture provides a suitable alkaline environment to help the modified active agent better exert its dissolution effect on the unexposed photoresist and avoid alkaline corrosion of the exposed photoresist, achieving high-selectivity development; the modified active agent can increase the solubility of the organic components in the photoresist in the developer, while the weak alkaline mixture can react with the acidic groups in the photoresist to form substances that are more soluble in the developer. The combination of the two expands the dissolution range of the developer and improves the overall dissolution ability of the developer for the unexposed photoresist. Finally, there is no residue of the unexposed photoresist.

[0028] 2. The present invention improves the defoaming performance of the developer and thus the development effect by preparing a modified defoamer and adding a composite dispersant. During the development process, due to the interaction between the developer and the photoresist and the mixing of air, etc., foam is easily generated. The foam will hinder the full contact between the developer and the photoresist and affect the development effect. The modified defoamer prepared by grafting reaction can quickly reduce the surface tension of the foam liquid film, causing the foam to break, thereby effectively eliminating the foam in the developer and ensuring that the developer can act evenly on the surface of the photoresist; during the development process, fragments will be generated after the photoresist is dissolved by the developer. The composite dispersant can adsorb on the surface of the photoresist fragments, making their surfaces carry the same charge. Through electrostatic repulsion, the fragments are evenly dispersed in the developer, preventing the fragments from re-aggregating or depositing on the surface of the photoresist and avoiding defects in the developed pattern and improving the development quality. After the modified defoamer eliminates the foam, it provides a good environment for the composite dispersant to better exert its dispersion effect and avoids the interference of the foam on the dispersion effect. The foam height of the developer is 0.12 cm.

[0029] 3. In the developer of the present invention, a modified chelating agent and an organic solvent are added. The synergistic effect between the two can improve the developing effect of the material, and the pattern on the material is clear, complete and has no burrs. During the developing process, metal ion impurities may be introduced by the photoresist or equipment, and these impurities will affect the developing effect and the performance of the photoresist. The modified chelating agent prepared by the cross-linking reaction can form a stable chelate with metal ions, remove metal ions from the developer or reduce their activity, prevent adverse reactions between metal ions and the components of the photoresist or developer, and improve the developing quality; the organic solvent has good solubility and can dissolve the organic components in the photoresist, making the photoresist easier to be removed in the developer, and can dissolve the organic components in the photoresist, making the photoresist easier to be removed in the developer; the modified chelating agent removes metal ion impurities, which can prevent metal ions from reacting with the organic solvent or affecting the solubility of the organic solvent, improve the dissolution effect of the organic solvent on the photoresist, and the organic solvent provides a good dissolution environment for the modified chelating agent, enabling the modified chelating agent to be better dispersed in the developer and fully exert its chelating effect.

[0030] 4. The developer of the present invention is applied to the developing process, and the pH value and process parameters are adjusted, so as to improve the developing effect and efficiency of the material. Finally, the material develops quickly, has a good effect and has no burrs. A weakly alkaline mixture with too high a concentration may damage the cured photoresist and the substrate, such as corroding the surface of the substrate or destroying the performance of the photoresist. By controlling its concentration, while effectively removing the unexposed photoresist, it is possible to avoid adverse effects on the exposed photoresist and the substrate, ensure the adhesion between the photoresist and the substrate and the integrity of the photoresist pattern; the organic solvent is mainly used to dissolve the photoresist, and its concentration determines the dissolution ability of the photoresist. As the concentration increases, the dissolution effect on the photoresist is enhanced, and the unexposed photoresist can be removed more quickly and thoroughly, but too high a concentration may cause excessive dissolution of the photoresist, and even dissolve the exposed part of the photoresist, affecting the formation of the photolithography pattern; too low a concentration cannot effectively dissolve the photoresist, resulting in incomplete development. Controlling the parameters of the spray can make the developer better penetrate into the microstructures of the photoresist, enhance the contact and interaction between the developer and the photoresist, accelerate the developing reaction speed, and ensure that the unexposed photoresist can be quickly and fully dissolved and removed; controlling the temperature of the oven can cause a certain degree of rearrangement of the inert components of the exposed photoresist in the polymerization network and fill the holes that may be eroded by the developer. Description of the Drawings

[0031] Figure 1 It is the foam height diagram of Example 20 and Comparative Examples 7-10 in the present invention. Detailed Embodiments

[0032] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.

[0033] Specifically refer to Figure 1 , the present invention provides a developer and a developing process for high selectivity of alkali-soluble photoresist, and the technical solutions are as follows:

[0034] Example 1

[0035] Prepare a modified active agent:

[0036] Put 8 parts of sodium dodecylbenzenesulfonate and 3 parts of ferrous sulfate into a mixed solution of methanol and deionized water, stir for 30 min to obtain a mixed solution; add 2 parts of hydrogen peroxide to the mixed solution, control the stirring temperature at 50 °C, and the stirring time at 3 h. After the reaction is completed, centrifuge at a speed of 5000 rpm, and vacuum-dry the centrifuged solid at 60 °C for 12 h to obtain a modified active agent; the weight ratio of methanol to deionized water is 1:2.

[0037] Prepare a weakly alkaline mixture:

[0038] Mix sodium dihydrogen phosphate, sodium metaborate and ethylenediamine, and the weight ratio of sodium dihydrogen phosphate, sodium metaborate and ethylenediamine is 3:2:1.

[0039] Prepare a modified defoamer:

[0040] Put 6 parts of polydimethylsiloxane and 5 parts of fatty alcohol polyoxyethylene ether into 15 parts of toluene, stir for 20 min until completely dissolved to obtain solution A; add 3 parts of benzoyl peroxide to solution A, stir for 1 h and then transfer to a hydrothermal reaction kettle, react at 85 °C for 5 h, and obtain a modified defoamer by centrifugal drying after the reaction is completed.

[0041] Prepare a composite dispersant:

[0042] Mix polyvinylpyrrolidone, sodium polyacrylate and cetyltrimethylammonium bromide, and the weight ratio of polyvinylpyrrolidone, sodium polyacrylate and cetyltrimethylammonium bromide is 1:1:1.

[0043] Prepare a modified chelating agent:

[0044] Dissolve 10 parts of disodium ethylenediaminetetraacetate and 5 parts of diethylenetriaminepentaacetic acid in 20 parts of deionized water, and stir for 25 min to obtain a mixed solution A; dissolve 3 parts of diethylenetriamine in 5 parts of deionized water, and stir for 15 min to obtain a mixed solution B; under stirring conditions, slowly add the mixed solution B to the mixed solution A, adjust the pH value of the reaction system to 8 with sodium hydroxide solution, stir and react at 60 °C for 7 h, and after the reaction, centrifuge and dry to obtain a modified chelating agent.

[0045] The developer is obtained by mixing the above materials by mass percentage.

[0046] Developing process:

[0047] S1 Prepare the developer well, place it in a constant-temperature storage container, and adjust the temperature of the developer to 10 °C; place the exposed sample stably on the operating table, set the spray pressure to 60 kPa, the spray angle to 80°, and the moving speed of the nozzle to 130 mm / s. After spraying, a semi-developed sample is obtained;

[0048] S2 After development, immediately rinse the semi-developed sample with deionized water to remove the residual developer and dissolved photoresist on the surface; then blow dry with nitrogen, control the nitrogen flow rate at 1.5 L / min to obtain a dry sample; place the dry sample in an oven and treat it at 80 °C for 1 h to obtain a developed sample.

[0049] Examples 2-9

[0050] Refer to the parameter conditions in Example 1, and the specific differences are shown in Table 1.

[0051] Table 1 Parameter conditions of Examples 1-9

[0052]

[0053] Comparative Example 1 Refer to the parameter conditions in Example 1, the difference is that no modified activator is added.

[0054] Comparative Example 2 Refer to the parameter conditions in Example 1, the difference is that only sodium dodecylbenzenesulfonate is added as an activator.

[0055] Comparative Example 3 Refer to the parameter conditions in Example 1, the difference is that only sodium dihydrogen phosphate is added as a weak alkaline agent.

[0056] Comparative Example 4 Refer to the parameter conditions in Example 1, the difference is that only sodium metaborate is added as a weak alkaline agent.

[0057] Comparative Example 5 Refer to the parameter conditions in Example 1, the difference is that only ethylenediamine is added as a weak alkaline agent.

[0058] Comparative Example 6 The parameters and conditions in Example 1 are referred to, except that sodium hydroxide is added as a strong alkaline agent.

[0059] Example 10 Photoresist solubility test

[0060] The substrate was observed under a 1000x scanning electron microscope to see whether there was any photoresist residue in the areas with and without pixels. ◎: no residue, ○: a small amount of residue or a large amount of erosion, △: a large amount of residue or a small amount of erosion, ●: no erosion. The results are shown in Table 2.

[0061] Table 2 Photoresist solubility test of Examples 1-9 and Comparative Examples 1-6

[0062]

[0063] It can be found from Table 2 that in Examples 1-7 and Comparative Examples 1-2, when no modified activator is added, the surface tension of the developer is very large, and it is difficult for the unexposed photoresist to completely contact the developer, and at this time, a large amount of unexposed photoresist remains; when the sodium dodecylbenzene sulfonate is not subjected to a hydroxylation reaction, the surface tension of the developer decreases to a certain extent, but the effect is still not good, and unexposed photoresist still remains; when the modified activator is added to the developer and the mass percentage is controlled, the amount of unexposed photoresist residue gradually decreases. This is because the modified activator can reduce the interfacial tension between the photoresist and the developer, making it easier for the developer to penetrate into the unexposed photoresist, and its special functional group can also interact with the photoresist molecules to destroy the force between the photoresist molecules, thereby increasing the dissolution rate of the unexposed photoresist in the developer. In Examples 8-9 and Comparative Examples 3-6, when a weak alkaline agent is selected and added to the developer, the alkaline environment at this time cannot dissolve the unexposed photoresist well, so that it still has a certain amount of residue; when sodium hydroxide is added as a strong alkaline agent, although the unexposed photoresist is completely removed at this time, the photoresist of the exposed part is also affected, and a large amount of corrosion occurs, which affects the final development effect; after adding the weak alkaline mixture, it provides a suitable alkaline environment, helps the modified active agent to better play a role in dissolving the unexposed photoresist, and avoids alkaline corrosion to the exposed photoresist, so as to achieve highly selective development. The modified active agent can increase the solubility of the developer to the organic components in the photoresist, and the weak alkaline mixture can react with the acidic groups in the photoresist to generate substances that are more soluble in the developer. The combination of the two expands the solubility range of the developer and improves the overall solubility of the developer to the unexposed photoresist.

[0064] Examples 11-21

[0065] Referring to the parameter conditions in Example 8, the difference is that the preparation parameters and mass percentages of the modified defoamer and the composite dispersant are changed, as shown in Table 3.

[0066] Table 3 Parameter conditions of Example 8 and Examples 11 - 21

[0067]

[0068] Comparative Example 7 Refer to the parameter conditions in Example 8, the difference is that the modified defoamer is not added.

[0069] Comparative Example 8 Refer to the parameter conditions in Example 8, the difference is that only polydimethylsiloxane is added as the defoamer.

[0070] Comparative Example 9 Refer to the parameter conditions in Example 8, the difference is that the composite dispersant is not added.

[0071] Comparative Example 10 Refer to the parameter conditions in Example 8, the difference is that only polyvinylpyrrolidone is added as the dispersant.

[0072] Example 22 Defoaming performance test

[0073] Put 30 ml of developer in a 100 ml test tube, shake it vertically for 30 min, measure the foam height. The results are shown in Table 4, and the foam height diagrams of Example 20 and Comparative Examples 7 - 10 are as Figure 1 shown.

[0074] Table 4 Defoaming performance test of Example 8, Examples 11 - 21 and Comparative Examples 7 - 10

[0075]

[0076] From Table 4 and Figure 1It can be found that in Examples 8, 11 - 16 and Comparative Examples 7 - 8, when the modified defoamer is not added, the defoaming performance of the developer is very poor. This is because during the development process, due to the interaction between the developer and the photoresist and the mixing of air, etc., foam is easily generated. The foam will hinder the full contact between the developer and the photoresist, affecting the development effect. When only polydimethylsiloxane is added as the defoamer, although the defoaming performance of the developer is improved to some extent, the effect is still very poor. When the modified defoamer is added and the preparation parameters are changed, the defoaming performance of Example 15 is the best, and the foam height is only 0.42 cm. This is because the modified defoamer prepared through the grafting reaction can quickly reduce the surface tension of the foam liquid film, causing the foam to break, thereby effectively eliminating the foam in the developer and ensuring that the developer can act uniformly on the surface of the photoresist. In Examples 17 - 21 and Comparative Examples 9 - 10, when the composite dispersant is not added, the foam height of the developer is relatively high. When only polyvinylpyrrolidone is added as the dispersant, it does not have a great promoting effect on the defoaming effect of the developer. However, after adding the composite dispersant, the defoaming performance is improved, and the foam height of Example 20 is only 0.12 cm. This is because during the development process, when the photoresist is dissolved by the developer, fragments will be generated. The composite dispersant can adsorb on the surface of the photoresist fragments, making their surfaces carry the same charge. Through the electrostatic repulsion effect, the fragments are evenly dispersed in the developer, preventing the fragments from re-aggregating or depositing on the surface of the photoresist, avoiding defects in the developed pattern, and improving the development quality. Through comparison, it can be found that there is a certain synergistic effect between the modified defoamer and the composite dispersant. After the modified defoamer eliminates the foam, it provides a good environment for the composite dispersant to better play its dispersing role, avoiding the interference of the foam on the dispersing effect.

[0077] Examples 23 - 33

[0078] Referring to the parameter conditions in Example 20, the difference lies in changing the preparation parameters and mass percentages of the modified chelating agent and the selection of the organic solvent, as shown in Table 5 specifically.

[0079] Table 5 Parameter Conditions of Example 20 and Examples 23 - 33

[0080]

[0081] Comparative Example 11 Referring to the parameter conditions in Example 20, the difference lies in not adding the modified chelating agent.

[0082] Comparative Example 12 Referring to the parameter conditions in Example 20, the difference lies in only adding disodium ethylenediaminetetraacetate as the chelating agent.

[0083] Example 34 Development Effect Test

[0084] The development effects of Examples 20, 23 - 33 and Comparative Examples 11 - 12 were directly observed under a microscope. (1) Whether the developed pattern was clear and complete, ○: the image was clear and complete, ×: underdevelopment or overdevelopment, and the pattern was difficult to distinguish; (2) Whether there was a burr phenomenon at the edge of the pattern, ○: the edge of the pattern was clear, ×: there were burrs or defects at the edge of the pattern. The obtained results are shown in Table 6.

[0085] Table 6 Development Effect Test of Examples 20, 23 - 33 and Comparative Examples 11 - 12

[0086]

[0087] It can be found from Table 6 that in Examples 20, 23 - 28 and Comparative Examples 11 - 12, when no modified chelating agent was added or only disodium ethylenediaminetetraacetate was added as a chelating agent, the final material pattern was not clear and burrs appeared, and the development effect was poor. Because during the development process, metal ion impurities may be introduced by the photoresist or equipment, and these impurities will affect the development effect and the performance of the photoresist; when the modified chelating agent was added, although there were still some burrs, the pattern became clear. This is because the modified chelating agent prepared by the cross - linking reaction can form stable chelates with metal ions, removing the metal ions from the developer or reducing their activity, preventing adverse reactions between metal ions and the components of the photoresist or developer, and improving the development quality. In Examples 29 - 33, the type of organic solvent was changed, and Example 32 presented the best development effect, with a clear pattern and no burrs. This is because the organic solvent has good solubility, can dissolve the organic components in the photoresist, making the photoresist easier to be removed in the developer, and can dissolve the organic components in the photoresist, making the photoresist easier to be removed in the developer. And there is also a synergistic effect between the organic solvent and the modified chelating agent. The modified chelating agent removes metal ion impurities, which can prevent metal ions from reacting with the organic solvent or affecting the solubility of the organic solvent, improving the dissolution effect of the organic solvent on the photoresist, while the organic solvent provides a good dissolution environment for the modified chelating agent, enabling the modified chelating agent to be better dispersed in the developer and fully exert its chelating effect.

[0088] Examples 35 - 46

[0089] Referring to the parameter conditions in Example 32, the difference was that the mass percentages of the weak - alkaline mixture and the organic solvent and the parameters of the development process were changed, as shown in Table 7 specifically.

[0090] Table 7 Parameter Conditions of Example 32 and Examples 35 - 46

[0091]

[0092] Comparative Example 13 Refer to the parameter conditions in Example 32, with the difference that the mass percentage of the weakly alkaline mixture is 20%.

[0093] Comparative Example 14 Refer to the parameter conditions in Example 32, with the difference that the mass percentage of the organic solvent is 30%.

[0094] Comparative Example 15 Refer to the parameter conditions in Example 32, with the difference that the mass percentage of the organic solvent is 1%.

[0095] Comparative Example 16 Refer to the parameter conditions in Example 32, with the difference that the spraying pressure is 120 kPa.

[0096] Comparative Example 17 Refer to the parameter conditions in Example 32, with the difference that the spraying pressure is 20 kPa.

[0097] Comparative Example 18 Refer to the parameter conditions in Example 32, with the difference that the temperature in the oven is 40 °C.

[0098] Example 47 Development effect and efficiency test

[0099] Use the same test method as in Example 34 to test the development effects of Examples 32, 35 - 46 and Comparative Examples 13 - 18, and measure their development times. ○: less than 15 minutes, high development efficiency; △: 15 - 45 minutes, general development efficiency; ×: more than 45 minutes, poor development efficiency. The results are shown in Table 8.

[0100] Table 8 Development effect and efficiency test of Examples 32, 35 - 46 and Comparative Examples 13 - 18

[0101]

[0102] As can be seen from Table 8, in Examples 32, 35 - 36 and Comparative Example 13, when the mass percentage content of the weak alkaline mixture is relatively high, the weak alkaline mixture with too high a concentration may cause damage to the cured photoresist and the substrate, such as corroding the surface of the substrate or damaging the performance of the photoresist; controlling its concentration in the examples can effectively remove the unexposed photoresist while avoiding adverse effects on the exposed photoresist and the substrate, ensuring the adhesion between the photoresist and the substrate and the integrity of the photoresist pattern. In Examples 37 - 38 and Comparative Examples 14 - 15, the organic solvent is mainly used to dissolve the photoresist, and its content determines the dissolution ability of the photoresist. When the concentration increases, the dissolution effect on the photoresist is enhanced, and the unexposed photoresist can be removed more quickly and thoroughly. The development effect of Example 37 is the best and the efficiency is the highest; however, too high a concentration may cause excessive dissolution of the photoresist, and even dissolve the exposed part of the photoresist, affecting the formation of the photolithography pattern; too low a concentration cannot effectively dissolve the photoresist, resulting in incomplete development. The weak alkaline mixture can react with the acidic components in the photoresist to promote the dissolution of the photoresist. The organic solvent can penetrate into the interior of the photoresist, reduce the cohesive force of the photoresist, and make the molecular chains of the photoresist easier to separate. Controlling the mass percentage content of the two creates better conditions for the reaction between the weak alkaline mixture and the photoresist, accelerating the dissolution rate of the weak alkaline mixture on the photoresist, and thus effectively improving the development efficiency. In Examples 39 - 46 and Comparative Examples 16 - 17, when the spray pressure is too high, due to the too large impact force of the developer, the exposed photoresist may be over-dissolved and removed. Overdevelopment will make the lines of the photolithography pattern thinner, the shape distorted, and damage the integrity of the pattern; when the spray pressure is too low, under a small pressure, the dissolution and rinsing effect of the developer on the photoresist is weak, the development speed is reduced, and it is difficult to meet the requirements of the process time in large-scale production, reducing the production efficiency; controlling the spray parameters can make the developer better penetrate into the microstructures of the photoresist, enhance the contact and interaction between the developer and the photoresist, accelerate the development reaction speed, and ensure that the unexposed photoresist can be quickly and fully dissolved and removed; controlling the temperature of the oven can cause a certain degree of rearrangement of the inert components of the exposed photoresist in the polymerization network, filling the holes that may be eroded by the developer. Too low a temperature is likely to cause uneven development.

[0103] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made in these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A developer for an alkali-soluble photoresist, characterized in that: In terms of mass percentage, the synthesis raw materials of the developer include the following components: Modified active agent: 8% - 12%; Weak alkaline mixture: 5% - 7%; Modified defoaming agent: 3% - 5%; Composite dispersant: 1% - 3%; Modified chelating agent: 1% - 3%; Organic solvent: 9% - 15%; Deionized water: the balance; the total mass percentage is 100%; The modified active agent is prepared from sodium dodecylbenzenesulfonate, ferrous sulfate and hydrogen peroxide; the modified defoaming agent is prepared from polydimethylsiloxane, fatty alcohol polyoxyethylene ether and benzoyl peroxide; the composite dispersant includes polyvinylpyrrolidone, sodium polyacrylate and cetyltrimethylammonium bromide; the modified chelating agent is prepared from disodium ethylenediaminetetraacetate, diethylenetriaminepentaacetic acid and diethylenetriamine.

2. The developer for the alkali-soluble photoresist according to claim 1, characterized in that: The preparation method of the modified active agent is as follows: put 8 parts of the sodium dodecylbenzenesulfonate and 3 parts of the ferrous sulfate into a mixed solution of methanol and deionized water, and stir for 30 min to obtain a mixed solution A; add 2 parts of the hydrogen peroxide to the mixed solution A, control the stirring temperature at 50°C - 90°C, and the stirring time at 3 h - 5 h. After the reaction is completed, centrifuge at 5000 rpm, and vacuum-dry the centrifuged solid at 60°C for 12 h to obtain the modified active agent; the weight ratio of the methanol to the deionized water is 1:

2.

3. The developer for an alkali-soluble photoresist according to claim 1, characterized in that: The weak alkaline mixture is a mixture of sodium dihydrogen phosphate, sodium metaborate and ethylenediamine, and the weight ratio of the sodium dihydrogen phosphate, the sodium metaborate and the ethylenediamine is 3 - 5:2:

1.

4. The developer for an alkali-soluble photoresist according to claim 1, characterized in that: The preparation method of the modified defoaming agent is as follows: put 6 parts of the polydimethylsiloxane and 5 parts of the fatty alcohol polyoxyethylene ether into 15 parts of toluene, and stir for 20 min until completely dissolved to obtain a solution A; add 3 parts of the benzoyl peroxide to the solution A, stir for 1 h, then transfer it to a hydrothermal reaction kettle, and react at 85°C - 105°C for 5 h - 7 h. After the reaction is completed, obtain the modified defoaming agent by centrifugal drying.

5. The developer for an alkali-soluble photoresist according to claim 1, characterized in that: The composite dispersant is a mixture of the polyvinylpyrrolidone, the sodium polyacrylate and the cetyltrimethylammonium bromide, and the weight ratio of the polyvinylpyrrolidone, the sodium polyacrylate and the cetyltrimethylammonium bromide is 1 - 2:1:1 - 2.

6. The developer for an alkali-soluble photoresist according to claim 1, wherein: The preparation method of the modified chelating agent is as follows: dissolve 10 parts of the disodium ethylenediaminetetraacetate and 5 parts of the diethylenetriaminepentaacetic acid in 20 parts of deionized water, and stir for 25 min to obtain a mixed solution A; dissolve 3 parts of the diethylenetriamine in 5 parts of deionized water, and stir for 15 min to obtain a mixed solution B; under stirring conditions, slowly drop the mixed solution B into the mixed solution A, adjust the pH value of the reaction system to 8 with sodium hydroxide solution, and stir and react at a temperature of 60°C - 80°C for 7 h - 9 h. After the reaction is completed, obtain the modified chelating agent by centrifugal drying.

7. The developer for an alkali-soluble photoresist according to claim 1, wherein: The organic solvent is one or two of methanol, ethanol and N,N-dimethylformamide.

8. A developing process for an alkali-soluble photoresist, characterized in that: Use the developer as described in claim 1 and apply it to the development process. The specific steps are as follows: S1 Prepare the developer well and place it in a constant-temperature storage container. Adjust the temperature of the developer to 10°C - 15°C. Place the exposed sample steadily on the operating table. Set the spraying pressure to 60 kPa - 80 kPa, the spraying angle to 80°, and the moving speed of the nozzle to 130 mm / s - 170 mm / s. After spraying, a semi-developed sample is obtained. S2 After development, immediately rinse the semi-developed sample with deionized water to remove the residual developer and dissolved photoresist on the surface. Then, dry it with nitrogen, and control the nitrogen flow rate at 1.5 L / min to obtain a dry sample. Place the dry sample in an oven and process it at 80°C - 100°C for 1 h to obtain a developed sample.

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