Developing solution with high selectivity for alkali-soluble photoresist and developing process

Abstract

The invention relates to the technical field of developing, in particular to a high-selectivity developing solution for alkali-soluble photoresist and a developing process. The problem that the developing effect and the dissolving effect are poor in the developing process is solved. The developing solution is prepared from the following synthetic raw materials: a modified active agent, a weakly alkaline mixture, a modified defoaming agent, a composite dispersing agent, an improved chelating agent, an organic solvent and deionized water. According to the invention, the dissolution rate of the unexposed photoresist is improved by preparing the modified active agent and the weakly alkaline mixture, and the high selectivity of the developing solution is embodied; the defoaming performance of the developing solution is improved by preparing the modified defoaming agent and adding the composite dispersing agent; the developing effect of the material can be improved through the synergistic effect of the improved chelating agent and the organic solvent in the developing solution; the developing solution is applied to the developing process, and the pH value and process parameters are adjusted, so that the developing effect and efficiency of the material are improved.

Description

Technical Field

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

[0002] Alkali-soluble negative photoresist is composed of a pigment dispersion, a solvent, a photosensitive resin and related additives. The short-chain molecules containing polymers will be cross-linked into long-chain molecules due to light. Generally, a certain thickness of photoresist is first formed on a glass substrate or base material by coating, and then after exposure, it is developed with a developer to remove the unexposed photoresist to obtain the required image. In this process, the alkali-soluble negative photoresist will solidify in the exposed area, while the non-exposed area will maintain its original shape and can be easily removed in the developer. Generally speaking, alkali-soluble negative photoresist is acidic, even after solidification, so if the development process is not specially designed, it will affect the solidified part.

[0003] At present, the spray developing equipment is basically used in the developing process. The developing time is controlled by controlling the running speed of the equipment. After the developing stage is completed, the residual developer and photoresist are thoroughly rinsed through the water washing process to ensure the product's developing quality. The macromolecular photoresist particles after the developer and photoresist react are hydrophobic. If the developer has poor solubility, it will cause the photoresist particles to agglomerate, causing abnormalities, and in severe cases, it will clog the filter element. Alkali-soluble negative photoresist has a small chemical difference between its uncured and cured forms, so the development process can easily cause some of the cured glue to be removed, or pinholes to appear.

[0004] Therefore, the current development process still has problems with poor development effect and dissolution effect, which limits its development in the development field.

[0005] Therefore, a developer and a development process with high selectivity for alkali-soluble photoresist are proposed. Summary of the invention

[0006] The purpose of the present invention is to design a developer and a development process with high selectivity for alkali-soluble photoresist. The synthetic raw materials of the developer in the present invention include a modified active agent, 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 unexposed photoresist by preparing a modified active agent and a weak alkaline mixture, thereby reflecting the high selectivity of the developer; the defoaming performance of the developer is improved by preparing a modified defoamer and adding a composite dispersant; the modified chelating agent in the developer synergistically acts with the organic solvent to improve the development effect of the material; the developer is applied to the development process, and the pH and process parameters are adjusted, thereby improving the development effect and efficiency of the material.

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

[0008] In one aspect, the present invention provides a developer with high selectivity for alkali-soluble photoresist. The synthetic raw materials of the developer include the following components in percentage by mass:

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

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

[0011] Modified defoamer: 3%-5%;

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

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

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

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

[0016] Preferably, the preparation method of the modified active agent is: 8 parts of sodium dodecylbenzene sulfonate and 3 parts of ferrous sulfate are put into a mixed solution of methanol and deionized water, and stirred for 30 minutes to obtain a mixed solution A; 2 parts of hydrogen peroxide are added to the mixed solution A, and the stirring temperature is controlled to be 50°C-90°C, and the stirring time is 3h-5h. After the reaction is completed, centrifugation is performed at a speed of 5000rpm, and the solid obtained by centrifugation is vacuum dried at 60°C for 12h to obtain a 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 defoamer is as follows: 6 parts of polydimethylsiloxane and 5 parts of fatty alcohol polyoxyethylene ether are put into 15 parts of toluene, and stirred for 20 minutes until completely dissolved to obtain solution A; 3 parts of benzoyl peroxide are added to solution A, and after stirring for 1 hour, the solution is transferred to a hydrothermal reactor, reacted at 85°C-105°C for 5h-7h, and after the reaction is completed, the modified defoamer is obtained by centrifugal drying.

[0019] Preferably, the composite dispersant is a mixture of polyvinyl pyrrolidone, sodium polyacrylate and cetyl trimethyl ammonium bromide, and the weight ratio of polyvinyl pyrrolidone, sodium polyacrylate and cetyl trimethyl ammonium 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 minutes to obtain a mixed solution A; dissolve 3 parts of diethylenetriamine in 5 parts of deionized water, and stir for 15 minutes to obtain a mixed solution B; under stirring, slowly dropwise 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 the reaction at a temperature of 60°C-80°C for 7h-9h, and centrifugally dry after the reaction to obtain the modified chelating agent.

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

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

[0023] Another aspect of the present invention provides a highly selective developing process for alkali-soluble photoresist, wherein the above-mentioned developer is applied to the developing process, and the specific steps are as follows:

[0024] S1 prepares the developer and places it in a constant temperature storage container, adjusting the temperature of the developer to 10℃-15℃; stably place the exposed sample on the operating table, set the spray pressure to 60kPa-80kPa, the spray angle to 80°, and the nozzle moving speed to 130mm / s-170mm / s, and obtain a semi-developed sample after spraying;

[0025] After S2 development is completed, the semi-developed sample is immediately rinsed with deionized water to remove the residual developer and dissolved photoresist on the surface; then it is blown dry with nitrogen, and the nitrogen flow rate is controlled at 1.5L / min to obtain a dry sample; the dry sample is placed in an oven and treated at 80℃-100℃ for 1h to obtain a developed sample.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] 1. The present invention improves the solubility of unexposed photoresist by preparing a mixture of a modified active agent and a weak base and changing the mass percentage of the modified active agent, thereby reflecting the high selectivity of the developer. The modified active agent obtained by hydroxylating sodium dodecylbenzene sulfonate 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 to destroy the forces between the photoresist molecules, 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 dissolve the unexposed photoresist and avoid alkaline corrosion of the exposed photoresist, thereby achieving highly selective development. The modified active agent can increase the solubility of the developer for 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 dissolution ability of the developer for the unexposed photoresist, so that there is no residue of the unexposed photoresist in the end.

[0028] 2. The present invention improves the defoaming performance of the developer by preparing a modified defoamer and adding a composite dispersant, thereby improving the development effect. During the development process, foam is easily generated due to the interaction between the developer and the photoresist and the mixing of air. The foam will hinder the full contact between the developer and the photoresist and affect the development effect. The modified defoamer prepared by the grafting reaction can quickly reduce the surface tension of the foam liquid film, break the foam, and thus effectively eliminate the foam in the developer, ensuring that the developer can act evenly on the surface of the photoresist; during the development process, the photoresist will produce fragments after being dissolved by the developer, and the composite dispersant can be adsorbed on the surface of the photoresist fragments, so that the surface has the same charge, and through the electrostatic repulsion, 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 development pattern, and improving the development quality. After the modified defoamer eliminates the foam, a good environment is provided for the composite dispersant to better play a dispersing role, avoiding the interference of the foam on the dispersing effect, and the foam height of the developer is 0.12cm.

[0029] 3. The present invention adds a modified chelating agent and an organic solvent to the developer, and the synergistic effect between the two can improve the development effect of the material, and the pattern on the material is clear, complete and has no burrs. During the development process, the photoresist or the equipment may introduce metal ion impurities, which will affect the development effect and the performance of the photoresist. The modified chelating agent prepared by the cross-linking reaction can form a stable chelate with the metal ions, remove the metal ions from the developer or reduce its activity, prevent the metal ions from reacting adversely with the photoresist or the developer components, and improve the development quality; the organic solvent has good solubility, can dissolve the organic components in the photoresist, make the photoresist easier to remove in the developer, and can dissolve the organic components in the photoresist, make the photoresist easier to remove in the developer; the modified chelating agent removes metal ion impurities, can prevent the 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, so that the modified chelating agent can be better dispersed in the developer and give full play to its chelating effect.

[0030] 4. The present invention applies developer to the development process, adjusts the pH and process parameters, thereby improving the development effect and efficiency of the material, and finally the material is developed quickly, effectively, and without burrs. A weakly alkaline mixture with too high a concentration may damage the solidified photoresist and substrate, such as corroding the substrate surface or destroying the performance of the photoresist. By controlling its concentration, it can effectively remove the unexposed photoresist while avoiding adverse effects on the exposed photoresist and substrate, ensuring 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 ability to dissolve 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 photolithographic pattern; too low a concentration cannot effectively dissolve the photoresist, resulting in incomplete development. Controlling the spray parameters can make the developer better penetrate into the tiny structure of the photoresist, enhance the contact and interaction between the developer and the photoresist, speed up the development reaction, and ensure that the unexposed photoresist can be quickly and fully dissolved and removed; controlling the temperature of the oven can make the inert components of the exposed photoresist rearrange to a certain extent in the polymer network, filling the holes that may be eroded by the developer. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0032] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] Specific reference Figure 1 The present invention provides a developer and a development process for alkaline-soluble photoresist with high selectivity, and the technical scheme is as follows:

[0034] Example 1

[0035] Preparation of modified active agent:

[0036] 8 parts of sodium dodecylbenzene sulfonate and 3 parts of ferrous sulfate are put into a mixed solution of methanol and deionized water, and stirred for 30 minutes to obtain a mixed solution; 2 parts of hydrogen peroxide are added to the mixed solution, and the stirring temperature is controlled to be 50°C, and the stirring time is 3 hours. After the reaction is completed, centrifugation is performed at a speed of 5000 rpm, and the solid obtained by centrifugation is vacuum dried at 60°C for 12 hours to obtain a modified active agent; the weight ratio of methanol to deionized water is 1:2.

[0037] Prepare the weak alkaline mixture:

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

[0039] Preparation of modified defoamer:

[0040] 6 parts of polydimethylsiloxane and 5 parts of fatty alcohol polyoxyethylene ether were put into 15 parts of toluene, and stirred for 20 minutes until completely dissolved to obtain solution A; 3 parts of benzoyl peroxide were added to solution A, and after stirring for 1 hour, the solution was transferred to a hydrothermal reactor and reacted at 85°C for 5 hours. After the reaction was completed, the modified defoamer was obtained by centrifugal drying.

[0041] Preparation of composite dispersant:

[0042] Polyvinyl pyrrolidone, sodium polyacrylate and cetyl trimethyl ammonium bromide are mixed, and the weight ratio of polyvinyl pyrrolidone, sodium polyacrylate and cetyl trimethyl ammonium bromide is 1:1:1.

[0043] Preparation of 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 minutes to obtain a mixed solution A; dissolve 3 parts of diethylenetriamine in 5 parts of deionized water and stir for 15 minutes to obtain a mixed solution B; under stirring, slowly add the mixed solution B dropwise to the mixed solution A, adjust the pH value of the reaction system to 8 with sodium hydroxide solution, stir the reaction at 60°C for 7 hours, and centrifuge and dry after the reaction to obtain a modified chelating agent.

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

[0046] Development process:

[0047] S1 prepares the developer and places it in a constant temperature storage container, adjusting the temperature of the developer to 10°C; stably place the exposed sample on the operating table, set the spray pressure to 60kPa, the spray angle to 80°, and the nozzle moving speed to 130mm / s, and obtain a semi-developed sample after spraying;

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

[0049] Embodiment 2-9

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

[0051] Table 1 Parameters and conditions of Examples 1-9

[0052]

[0053]

[0054] Comparative Example 1 refers to the parameter conditions in Example 1, except that no modifying active agent is added.

[0055] Comparative Example 2 refers to the parameter conditions in Example 1, except that only sodium dodecylbenzene sulfonate is added as the active agent.

[0056] Comparative Example 3 refers to the parameter conditions in Example 1, except that only sodium dihydrogen phosphate is added as a weak alkaline agent.

[0057] Comparative Example 4 refers to the parameter conditions in Example 1, except that only sodium metaborate is added as a weak alkaline agent.

[0058] Comparative Example 5 refers to the parameter conditions in Example 1, except that only ethylenediamine is added as a weak alkaline agent.

[0059] Comparative Example 6 refers to the parameter conditions in Example 1, except that sodium hydroxide is added as a strong alkaline agent.

[0060] Example 10 Photoresist solubility test

[0061] 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.

[0062] Table 2 Photoresist solubility test of Examples 1-9 and Comparative Examples 1-6

[0063]

[0064]

[0065] 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.

[0066] Examples 11-21

[0067] 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.

[0068] Table 3 Parameter conditions of Example 8 and Examples 11-21

[0069]

[0070]

[0071] Comparative Example 7 refers to the parameter conditions in Example 8, except that no modified defoaming agent is added.

[0072] Comparative Example 8 refers to the parameter conditions in Example 8, except that only polydimethylsiloxane is added as a defoaming agent.

[0073] Comparative Example 9 refers to the parameter conditions in Example 8, except that no composite dispersant is added.

[0074] Comparative Example 10 refers to the parameter conditions in Example 8, except that only polyvinyl pyrrolidone is added as a dispersant.

[0075] Example 22 Defoaming Performance Test

[0076] 30 ml of developer was placed in a 100 ml test tube and vertically shaken for 30 min. The foam height was measured. The results are shown in Table 4. The foam heights of Example 20 and Comparative Examples 7-10 are shown in Table 4. Figure 1 shown.

[0077] Table 4 Defoaming performance test of Example 8, Examples 11-21 and Comparative Examples 7-10

[0078]

[0079]

[0080] From Table 4 and Figure 1It can be found that in Example 8, Examples 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, foam is easily generated due to the interaction between the developer and the photoresist and the mixing of air. The foam will hinder the full contact between the developer and the photoresist and affect the development effect; when only polydimethylsiloxane is added as a defoamer, the defoaming performance of the developer is improved, but the effect is still very poor; when the modified defoamer is added and the preparation parameters are changed, Example 15 has the best defoaming performance, and the foam height is only 0.42 cm. This is because the modified defoamer prepared by the grafting reaction can quickly reduce the surface tension of the foam liquid film and cause the foam to burst, thereby effectively eliminating the foam in the developer and ensuring that the developer can act evenly on the photoresist surface. In Examples 17-21 and Comparative Examples 9-10, the foam height of the developer is relatively high without adding the composite dispersant; when only polyvinyl pyrrolidone is added as a dispersant, the defoaming effect of the developer is not greatly promoted; and 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 in the development process, the photoresist will produce fragments after being dissolved by the developer, and the composite dispersant can be adsorbed on the surface of the photoresist fragments, so that the surface has the same charge, and through the electrostatic repulsion, 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 development pattern, and improving the development quality. By comparison, it can be found that the modified defoamer and the composite dispersant have a certain synergistic effect. After the modified defoamer eliminates the foam, it provides a good environment for the composite dispersant to better exert its dispersing effect, avoiding the interference of the foam on the dispersing effect.

[0081] Embodiment 23-33

[0082] Referring to the parameter conditions in Example 20, the difference is that the preparation parameters and mass percentage of the modified chelating agent and the selection of the organic solvent are changed, as shown in Table 5.

[0083] Table 5 Parameter conditions of Example 20 and Examples 23-33

[0084]

[0085]

[0086] Comparative Example 11 refers to the parameter conditions in Example 20, except that no modified chelating agent is added.

[0087] Comparative Example 12 refers to the parameter conditions in Example 20, except that only disodium ethylenediaminetetraacetic acid is added as a chelating agent.

[0088] Example 34 Development Effect Test

[0089] The development effects of Example 20, Examples 23-33 and Comparative Examples 11-12 were directly observed under a microscope. (1) Whether the developed pattern is clear and complete, ○: the image is clear and complete, ×: insufficient or excessive development, the pattern is difficult to distinguish; (2) Whether there is burr on the edge of the pattern, ○: the edge of the pattern is clear, ×: the edge of the pattern has burrs or is incomplete. The results are shown in Table 6.

[0090] Table 6 Development effect test of Example 20, Examples 23-33 and Comparative Examples 11-12

[0091]

[0092]

[0093] It can be found from Table 6 that in Example 20, Examples 23-28 and Comparative Examples 11-12, when the modified chelating agent is not added or only disodium ethylenediaminetetraacetic acid is added as the chelating agent, the final material pattern is unclear and has burrs, and the development effect is poor, because during the development process, the photoresist or the equipment may introduce metal ion impurities, and these impurities will affect the development effect and the performance of the photoresist; when the modified chelating agent is added, although there are still some burrs, the pattern becomes clear, because the modified chelating agent prepared by the cross-linking reaction can form a stable chelate with the metal ions, remove the metal ions from the developer or reduce its activity, prevent the metal ions from reacting adversely with the photoresist or the developer components, and improve the development quality. In Examples 29-33, the type of organic solvent was changed, and Example 32 showed the best development effect, with a clear pattern and no burrs, because the organic solvent has good solubility, can dissolve the organic components in the photoresist, and make the photoresist easier to remove in the developer. There is also a synergistic effect between the organic solvent and the improved chelating agent. The improved chelating agent removes metal ion impurities, which can prevent the metal ions from reacting with the organic solvent or affecting the solubility of the organic solvent, and improves the dissolution effect of the organic solvent on the photoresist. The organic solvent provides a good dissolution environment for the improved chelating agent, so that the improved chelating agent can be better dispersed in the developer and give full play to its chelating effect.

[0094] Examples 35-46

[0095] Referring to the parameter conditions in Example 32, the difference is that the mass percentages of the weak alkaline mixture and the organic solvent and the parameters of the development process are changed, as shown in Table 7.

[0096] Table 7 Parameters and conditions of Example 32 and Examples 35-46

[0097]

[0098]

[0099] Comparative Example 13 refers to the parameter conditions in Example 32, except that the mass percentage of the weak alkaline mixture is 20%.

[0100] Comparative Example 14 refers to the parameter conditions in Example 32, except that the mass percentage of the organic solvent is 30%.

[0101] Comparative Example 15 refers to the parameter conditions in Example 32, except that the mass percentage of the organic solvent is 1%.

[0102] Comparative Example 16 refers to the parameter conditions in Example 32, except that the spray pressure is 120 kPa.

[0103] Comparative Example 17 refers to the parameter conditions in Example 32, except that the spray pressure is 20 kPa.

[0104] Comparative Example 18 refers to the parameter conditions in Example 32, except that the temperature in the oven is 40°C.

[0105] Example 47 Development Effect and Efficiency Test

[0106] The same testing method as Example 34 was used to test the development effects of Example 32, Examples 35-46 and Comparative Examples 13-18, and their development times were also tested: ○: less than 15 minutes, high development efficiency; △: 15-45 minutes, average development efficiency; ×: more than 45 minutes, poor development efficiency. The results are shown in Table 8.

[0107] Table 8 Development effect and efficiency test of Example 32, Examples 35-46 and Comparative Examples 13-18

[0108]

[0109]

[0110] It can be found from Table 8 that in Example 32, Example 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 concentration may cause damage to the cured photoresist and substrate, such as corroding the substrate surface or destroying the performance of the photoresist; in the embodiment, the concentration is controlled, while the unexposed photoresist is effectively removed, the adverse effects on the exposed photoresist and substrate are avoided, and the adhesion between the photoresist and the substrate and the integrity of the photoresist pattern are ensured. In Examples 37-38 and Comparative Examples 14-15, the organic solvent is mainly used to dissolve the photoresist, and its content determines the dissolving ability of the photoresist. When the concentration increases, the dissolving effect of 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; 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 photolithographic pattern; too low a concentration cannot effectively dissolve the photoresist, resulting in incomplete development. The weak alkaline mixture can undergo a neutralization reaction with the acidic components in the photoresist, thereby promoting the dissolution of the photoresist. The organic solvent can penetrate into the interior of the photoresist, reducing the cohesive force of the photoresist and making the molecular chains of the photoresist easier to separate. By controlling the mass percentage content of the two, the organic solvent creates better conditions for the reaction between the weak alkaline mixture and the photoresist, speeding up the dissolution rate of the weak alkaline mixture on the photoresist, thereby effectively improving the development efficiency. In Examples 39-46 and Comparative Examples 16-17, when the spray pressure is too high, the exposed photoresist may be excessively dissolved and removed due to the excessive impact force of the developer. Excessive development will cause the lines of the photolithographic pattern to become thinner and the shape to be distorted, thereby destroying the integrity of the pattern. When the spray pressure is too low, the developer has a weaker dissolving and flushing effect on the photoresist under a smaller pressure, and the development speed is reduced, making it difficult to meet the process time requirements in large-scale production, thereby reducing production efficiency. Controlling the spray parameters can enable the developer to better penetrate into the microstructure 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 the inert components of the exposed photoresist to rearrange to a certain extent in the polymer network and fill the holes that may be eroded by the developer. Too low a temperature can easily cause uneven development.

[0111] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A developer with high selectivity for alkaline soluble photoresist, characterized in that: The synthetic raw materials of the developer include the following components in percentage by mass: Modified active agent: 8%-12%; Weak alkaline mixture: 5%-7%; Modified defoamer: 3%-5%; Composite dispersant: 1%-3%; Improved chelating agent: 1%-3%; Organic solvent: 9%-15%; Deionized water: balance; the total mass percentage is 100%.

2. The developer with high selectivity for alkali-soluble photoresist according to claim 1, characterized in that: The preparation method of the modified active agent is as follows: 8 parts of sodium dodecylbenzene sulfonate and 3 parts of ferrous sulfate are put into a mixed solution of methanol and deionized water, and the mixed solution A is obtained after stirring for 30 minutes; 2 parts of hydrogen peroxide are added to the mixed solution A, the stirring temperature is controlled to be 50°C-90°C, the stirring time is 3h-5h, and after the reaction is completed, the reaction is centrifuged at a speed of 5000rpm, and the solid obtained by centrifugation is vacuum dried at 60°C for 12h to obtain the modified active agent; the weight ratio of the methanol to the deionized water is 1:

2.

3. The developer with high selectivity for 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 with high selectivity for alkali-soluble photoresist according to claim 1, characterized in that: The preparation method of the modified defoamer is as follows: 6 parts of polydimethylsiloxane and 5 parts of fatty alcohol polyoxyethylene ether are put into 15 parts of toluene, and stirred for 20 minutes until they are completely dissolved to obtain solution A; 3 parts of benzoyl peroxide are added to the solution A, and after stirring for 1 hour, the solution is transferred to a hydrothermal reactor, reacted at 85° C.-105° C. for 5 hours-7 hours, and after the reaction is completed, the modified defoamer is obtained by centrifugal drying.

5. The developer with high selectivity for alkali-soluble photoresist according to claim 1, characterized in that: The composite dispersant is a mixture of polyvinyl pyrrolidone, sodium polyacrylate and cetyl trimethyl ammonium bromide, and the weight ratio of the polyvinyl pyrrolidone, the sodium polyacrylate and the cetyl trimethyl ammonium bromide is 1-2:1:1-2.

6. The developer with high selectivity for alkali-soluble photoresist according to claim 1, characterized in that: The preparation method of the modified chelating agent comprises the following steps: dissolving 10 parts of disodium ethylenediaminetetraacetate and 5 parts of diethylenetriaminepentaacetic acid in 20 parts of deionized water, and stirring for 25 minutes to obtain a mixed solution A; dissolving 3 parts of diethylenetriamine in 5 parts of deionized water, and stirring for 15 minutes to obtain a mixed solution B; slowly dropping the mixed solution B into the mixed solution A under stirring conditions, adjusting the pH value of the reaction system to 8 with a sodium hydroxide solution, stirring the reaction at a temperature of 60°C-80°C for 7h-9h, and centrifugally drying after the reaction to obtain the modified chelating agent.

7. The developer with high selectivity for alkali-soluble photoresist according to claim 1, characterized in that: The organic solvent is one or two of methanol, ethanol and N,N-dimethylformamide.

8. A highly selective developing process for alkali-soluble photoresist, characterized in that: The developer according to claim 1 is used in the development process, and the specific steps are as follows: S1 prepares the developer, places it in a constant temperature storage container, and adjusts the temperature of the developer to 10°C-15°C; stably places the exposed sample on the operating table, sets the spray pressure to 60kPa-80kPa, the spray angle to 80°, and the nozzle moving speed to 130mm / s-170mm / s, and obtains a semi-developed sample after spraying; After S2 development is completed, the semi-developed sample is immediately rinsed with deionized water to remove the developer and dissolved photoresist remaining on the surface; then, nitrogen is used for drying, and the nitrogen flow rate is controlled at 1.5L / min to obtain a dry sample; the dry sample is placed in an oven and treated at 80°C-100°C for 1h to obtain a developed sample.

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