Low-foaming developer additives for IC carrier development and their development methods

Abstract

This invention discloses a low-foaming developer additive for IC substrate development and its development method, relating to the field of IC substrate manufacturing technology. The low-foaming developer additive for IC substrate development comprises the following components in mass concentrations: accelerator 1.0-3.0%; wetting agent 1.0-3.0%; protectant 0.5-2.0%; chelating agent 1.5-3.5%; and defoaming agent 0.2-1.0%. This low-foaming developer additive for IC substrate development has advantages such as low foaming efficiency, precise development, stability, durability, and wide compatibility. It can be applied to the development process of IC substrates with a linewidth / spacing of 10μm, producing clear and complete patterns with low residual development rate.

Description

Technical Field

[0001] This invention relates to the field of IC substrate manufacturing technology, and in particular to a low-foaming developing additive for IC substrate development and a developing method thereof. Background Technology

[0002] With the rapid development of modern electronic technology, integrated circuit (IC) technology is accelerating its evolution towards higher integration, smaller size, and higher performance. As an indispensable component of integrated circuits, the IC substrate not only provides physical support for the chip and enables electrical interconnection, but also effectively protects the chip from damage caused by the external environment. Today, with the continuous increase in chip integration and the increasingly complex and precise manufacturing processes, extremely stringent requirements are placed on the manufacturing precision and line resolution of the IC substrate.

[0003] In IC substrate manufacturing, the developing process is a crucial step in photolithography. Its core function is to selectively remove photoresist from exposed areas through chemical dissolution, thereby achieving high-fidelity circuit pattern transfer. However, the persistent bubble defect problem in this process severely restricts process yield. Current developing additives easily induce microbubble nucleation during dynamic developing. These bubbles adsorb onto the substrate surface, forming localized barrier layers that hinder the interfacial reaction between the developer and photoresist, leading to defects such as uneven developing, pattern distortion, and critical dimensional deviations. According to industry statistics, bubble defects can cause a 10-20% yield loss in high-end substrate production, significantly increasing unit production costs. Furthermore, foam accumulation can lead to frequent equipment downtime for maintenance, reducing capacity utilization. Therefore, developing novel additives with low foaming properties and optimized developing performance has significant engineering application value for improving process yield and reducing overall costs.

[0004] Currently, there are several technical solutions regarding developer additives. For example, patent CN113093481A discloses a developer additive, its preparation method, and its application. This developer additive comprises modified cellulose salts, water-soluble derivatives of vitamin E, bentonite, and a solvent. It prevents further polymerization of unexposed substances, isolates and encapsulates these polymerized substances, and allows them to overflow from the tank, preventing them from adhering to the tank walls, rollers, pipes, and board surfaces. This keeps the tank clean, improves product yield, and reduces production costs. Patent CN113504715B discloses a printed circuit board developer additive. This additive comprises: a developer accelerator (3-15% by mass); a wetting agent (100-4000ppm by mass); and a copper surface stabilizer (50-2000ppm by mass). This developer additive can increase production speed by 20-40%, provides stable quality, significantly improves quality issues such as film residue back-adhesion, gaps, and incomplete development, has low operating costs, is environmentally friendly and pollution-free, and its waste liquid is easy to treat; it is non-toxic and harmless.

[0005] Existing developer additives can generally meet the needs of conventional PCB manufacturing processes. However, as IC substrate manufacturing moves towards higher precision and higher integration, the developing process becomes increasingly complex. Existing products have many shortcomings in low-foaming applications, severely restricting the further development of IC substrate manufacturing processes. First, ordinary additives are unable to quickly disrupt the stability of bubbles, leading to a large accumulation of bubbles and affecting developing uniformity. For example, due to insufficient defoaming ability of developer additives, the product development defect rate may soar from the original 5% to 15%. Second, ordinary additives may have negative effects on IC substrate developers, such as reducing the developing rate and disrupting the stability of the developer. This not only reduces production efficiency but may also potentially damage other properties of the IC substrate due to prolonged developing. Furthermore, it easily causes secondary pollution and residue problems. If these residues are not completely removed in subsequent cleaning processes, they will adversely affect subsequent processes of the IC substrate, such as electroplating and soldering, leading to poor soldering and increasing the product defect rate. Therefore, developing a low-foaming developer additive for IC substrate developing is of great significance. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a low-foaming developer additive for IC substrate development, along with its preparation and development methods, applicable to the development process of IC substrates. This low-foaming developer additive contains effective components such as accelerators, wetting agents, protectants, chelating agents, and defoamers. The accelerator is a substance containing two hydrophilic groups and two hydrophobic tail chains, with the hydrophilic groups linked by chemical bonds. It exhibits a lower critical micelle concentration and stronger ability to reduce the surface tension of the target solution, thus promoting the ionization of the developer and accelerating the development speed. The wetting agent accelerates the penetration of the developer additive components into the pores of the dry film, improving penetration efficiency. The protectant prevents the developer from being oxidized, extending its service life. The chelating agent chelates metal ions in the developing tank, preventing contamination of the effective components in the developer. The defoamer reduces the surface tension of the liquid, disrupts foam stability, and prevents or slows down the formation of bubbles.

[0007] First, this invention provides a low-foaming developer additive for IC carrier development, comprising the following components at the following mass concentrations:

[0008] Accelerator 1.0-3.0%;

[0009] Wetting agent 1.0-3.0%;

[0010] Protectant 0.5-2.0%;

[0011] Chelating agent 1.5-3.5%;

[0012] Defoamer 0.2-1.0%;

[0013] The accelerator has the structure of the following formula (1):

[0014] (1);

[0015] In equation (1), the degree of polymerization n = 2, 3, 4;

[0016] The wetting agent is selected from one or a mixture of more of the following: tetramethylfluorourea hexafluorophosphate (CAS No.: 678-41-1), tris(pentafluorophenyl) phosphate (CAS No.: 3806-34-6), and bis(2-(perfluorooctyl)ethyl) phosphate (CAS No.: 2795-39-3);

[0017] The protective agent is selected from one or a mixture of more of the following: bisphenol A dielyl ether (CAS No.: 3739-67-1), bisphenol A di(2,3-dihydroxypropyl) ether (CAS No.: 5581-32-8), and bisphenol A diglycidyl ether (CAS No.: 1675-54-3);

[0018] The chelating agent is selected from one or a mixture of more of the following: 4-mercaptobenzoic acid (CAS No.: 1074-36-8), 4-mercaptobutyric acid (CAS No.: 13095-73-3), and 2-mercaptobenzimidazole carboxylic acid (CAS No.: 58089-25-1);

[0019] The defoaming agent is selected from one or a mixture of more than one of N-phenylbenzylhydroxylamine, 2,4-dichlorobenzylhydroxylamine, and N-benzyl-N-hydroxyacetamide.

[0020] The preparation method of the accelerator in this invention is as follows: 2,5-di-tert-pentylhydroquinone, ethylene oxide, acetonitrile, triethylamine, and potassium hydroxide are placed in a high-pressure reactor. After the air in the reactor is vented, the temperature is raised to 80±2℃ and reacted for 45-50 hours. The mixture is then cooled to room temperature and the crude product is collected. The crude product is then subjected to rotary evaporation, dichloromethane solvent extraction, and drying to obtain the accelerator. By adjusting the molar ratio of 2,5-di-tert-pentylhydroquinone and ethylene oxide, accelerators with different degrees of polymerization (n) can be obtained. When the ratio is 1:4, n=2; when the ratio is 1:6, n=3; and when the ratio is 1:8, n=4.

[0021] In some specific embodiments, the preparation method of the accelerator is as follows: 0.4 mol of 2,5-ditert-pentylhydroquinone (CAS No.: 79-74-3) and 1.6 mol of ethylene oxide (CAS No.: 75-21-8) are added to a 5L high-pressure reactor, and 800 mL of acetonitrile (CAS No.: 75-05-8), 0.024 mol of triethylamine (CAS No.: 121-44-8) and 0.012 mol of potassium hydroxide (CAS No.: 1310-58-3) are added. The air in the reactor is discharged, the temperature is raised to 80℃ and reacted for 48 h, and then the temperature is lowered to room temperature to collect the crude product. The crude product is then subjected to rotary evaporation, dichloromethane (CAS No.: 75-09-2) solvent extraction and drying to obtain the accelerator with a degree of polymerization n of 2 as shown in the following formula (2);

[0022] (2).

[0023] In some specific embodiments, the preparation method of the accelerator is as follows: 0.4 mol of 2,5-ditert-pentylhydroquinone (CAS No.: 79-74-3) and 2.4 mol of ethylene oxide (CAS No.: 75-21-8) are added to a 5L high-pressure reactor, and 800 mL of acetonitrile (CAS No.: 75-05-8), 0.024 mol of triethylamine (CAS No.: 121-44-8) and 0.012 mol of potassium hydroxide (CAS No.: 1310-58-3) are added. The air in the reactor is discharged, the temperature is raised to 80℃ and reacted for 48 h, and then the temperature is lowered to room temperature to collect the crude product. The crude product is then subjected to rotary evaporation, dichloromethane (CAS No.: 75-09-2) solvent extraction and drying to obtain the accelerator with a degree of polymerization n of 3 as shown in the following formula (3);

[0024] (3).

[0025] In some specific embodiments, the preparation method of the accelerator is as follows: 0.4 mol of 2,5-ditert-pentylhydroquinone (CAS No.: 79-74-3) and 3.2 mol of ethylene oxide (CAS No.: 75-21-8) are added to a 5L high-pressure reactor, and 800 mL of acetonitrile (CAS No.: 75-05-8), 0.024 mol of triethylamine (CAS No.: 121-44-8) and 0.012 mol of potassium hydroxide (CAS No.: 1310-58-3) are added. The air in the reactor is discharged, the temperature is raised to 80℃ and reacted for 48 h, and then the temperature is lowered to room temperature to collect the crude product. The crude product is then subjected to rotary evaporation, dichloromethane (CAS No.: 75-09-2) solvent extraction and drying to obtain the accelerator with a degree of polymerization n of 4 as shown in the following formula (4).

[0026] (4).

[0027] Preferably, the low-foaming developer additive for IC carrier development comprises the following components at the following mass concentrations:

[0028] Accelerator 1.0-3.0%;

[0029] Wetting agent 1.0-3.0%;

[0030] Protectant 0.5-2.0%;

[0031] Chelating agent 1.5-3.5%;

[0032] Defoamer 0.2-1.0%;

[0033] The remainder is water.

[0034] The preparation method of the above-mentioned low-foaming developer additive for IC carrier development is as follows: weigh the promoter, wetting agent, protective agent, chelating agent and defoaming agent according to the required mass concentration, add them to water, mix evenly at room temperature, and store the resulting solution in a sealed container for later use.

[0035] The present invention also provides a developer containing the above-mentioned low-foaming developer additive for IC substrate development (hereinafter referred to as low-foaming developer additive).

[0036] Preferably, the developer contains 0.3-0.6% by mass of the aforementioned low-foaming developer additive.

[0037] This invention also provides a developing method for the developing process in IC substrate production; it includes the following developing stage 1 and developing stage 2 steps in sequence:

[0038] Developing Stage 1: The IC carrier is sprayed with developing solution from developing stage 1. The developing solution from developing stage 1 consists of sodium carbonate with a mass concentration of 1.0-1.5%, the aforementioned low-foaming developing additives at 0.4-0.6%, and the remainder water. The spraying pressure is 1.5 ± 0.5 kg / cm². 2 The spraying time is 30±5s;

[0039] Developing Stage 2: The IC substrate treated in Developing Stage 1 is sprayed with developing stage 2 developer solution; the developing stage 2 developer solution consists of 0.5-1.0% sodium carbonate (by mass), 0.3-0.4% of the aforementioned low-foaming developer additive, and the remainder water, with a spraying pressure of 1.5 ± 0.5 kg / cm². 2 The spraying time is 30±5s.

[0040] The function of the first developing stage is to quickly dissolve the unexposed dry film, allowing the circuit pattern to initially appear on the circuit board. The function of the second developing stage is to remove residual undeveloped material, making the circuit pattern clearer and more complete, improving the quality and precision of development, and ensuring that the circuit pattern on the circuit board meets the design requirements.

[0041] Preferably, the above-described developing method further includes a pre-immersion stage before the first developing stage: the exposed IC substrate is immersed in the pre-immersion solution for 15±2 seconds; the pre-immersion solution consists of sodium carbonate with a mass concentration of 0.4-0.6% and the remainder water. The purpose of the pre-immersion stage is to use sodium carbonate to fluff up the unexposed dry film, which helps the dry film to be quickly removed in the first and second developing stages.

[0042] In some specific embodiments, the developing method of the present invention sequentially includes the following steps: a pre-immersion stage, a developing stage 1, and a developing stage 2:

[0043] Pre-immersion stage: The exposed IC substrate is immersed in the pre-immersion solution for 15±2s; the pre-immersion solution consists of 0.5% sodium carbonate and the remainder water.

[0044] Developing Stage 1: The IC carrier is sprayed with developing solution from developing stage 1. The developing solution from developing stage 1 consists of 1.2% sodium carbonate (by mass), 0.6% of the aforementioned low-foaming developing additive, and the remainder water. The spraying pressure is 1.5 ± 0.5 kg / cm². 2 The spraying time is 30±5s;

[0045] Developing Stage 2: The IC substrate treated in Developing Stage 1 is sprayed with developing stage 2 developer solution; the developing stage 2 developer solution consists of 0.6% sodium carbonate (by mass), 0.3% of the aforementioned low-foaming developer additive, and the remainder water, with a spraying pressure of 1.5 ± 0.5 kg / cm². 2 The spraying time is 30±5s.

[0046] The low-foaming developer additive of the present invention for IC carrier development has the advantages of low foaming efficiency, precise development, stability and durability, and wide compatibility. It can be applied to the IC carrier development process with a line width / spacing of 10μm. After development, the pattern is clear and complete with low development residue, which is conducive to high-precision molding of IC carriers. The product has good stability and excellent compatibility with dry film and metal surfaces, which can reduce the IC carrier development defect rate and improve manufacturing efficiency. Attached Figure Description

[0047] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0048] Figure 1 The image shown under an optical microscope after development in Example 1;

[0049] Figure 2 The image shown in Example 4 is a developed pattern observed under an optical microscope after development.

[0050] Figure 3 The image shown in the optical microscope after development in Comparative Example 12 is a developed pattern observed after development.

[0051] Figure 4 This is the developed pattern observed under an optical microscope after development, as shown in Comparative Example 13. Detailed Implementation

[0052] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0053] It should be noted that the contents or concentrations mentioned in the following examples / comparative examples are all mass concentrations.

[0054] The preparation methods of the accelerators in Examples 1, 4, and 5 are as follows: 0.4 mol of 2,5-di-tert-pentylhydroquinone (CAS No.: 79-74-3) and 1.6 mol of ethylene oxide (CAS No.: 75-21-8) are added to a 5 L high-pressure reactor. 800 mL of acetonitrile (CAS No.: 75-05-8), 0.024 mol of triethylamine (CAS No.: 121-44-8), and 0.012 mol of potassium hydroxide (CAS No.: 1310-58-3) are added. The air in the reactor is purged, the temperature is raised to 80 °C, and the reaction is carried out for 48 h. The temperature is then lowered to room temperature, and the crude product is collected. The crude product is then subjected to rotary evaporation, solvent extraction with dichloromethane (CAS No.: 75-09-2), and drying to obtain the accelerator of this example with a degree of polymerization n of 2.

[0055] The preparation method of the accelerator in Example 2 is as follows: 0.4 mol of 2,5-di-tert-pentylhydroquinone (CAS No.: 79-74-3) and 2.4 mol of ethylene oxide (CAS No.: 75-21-8) are added to a 5L high-pressure reactor. 800 mL of acetonitrile (CAS No.: 75-05-8), 0.024 mol of triethylamine (CAS No.: 121-44-8), and 0.012 mol of potassium hydroxide (CAS No.: 1310-58-3) are added. The air in the reactor is purged, the temperature is raised to 80℃ and reacted for 48 h. The temperature is then lowered to room temperature and the crude product is collected. The crude product is then subjected to rotary evaporation, solvent extraction with dichloromethane (CAS No.: 75-09-2), and drying to obtain the accelerator with a degree of polymerization n of 3.

[0056] The preparation method of the accelerator in Example 3 is as follows: 0.4 mol of 2,5-di-tert-pentylhydroquinone (CAS No.: 79-74-3) and 3.2 mol of ethylene oxide (CAS No.: 75-21-8) are added to a 5L high-pressure reactor. 800 mL of acetonitrile (CAS No.: 75-05-8), 0.024 mol of triethylamine (CAS No.: 121-44-8), and 0.012 mol of potassium hydroxide (CAS No.: 1310-58-3) are added. The air in the reactor is purged, the temperature is raised to 80℃ and reacted for 48 h. The temperature is then lowered to room temperature and the crude product is collected. The crude product is then subjected to rotary evaporation, solvent extraction with dichloromethane (CAS No.: 75-09-2), and drying to obtain the accelerator with a degree of polymerization n of 4.

[0057] The preparation methods of the developer additives in Examples 1-5 are as follows: According to the formulas of Examples 1-5, the accelerator, wetting agent, protective agent, chelating agent, defoaming agent and the remaining water are weighed in sequence and added to the reaction vessel. The mixture is stirred and mixed at room temperature for 30 minutes to obtain the low-foaming developer additives of the corresponding examples. The obtained low-foaming developer additive solution is sealed and stored for later use.

[0058] Example 1:

[0059] The accelerator content is 2.0%, specifically... ;

[0060] The wetting agent content is 2.0%, specifically tetramethylfluorourea hexafluorophosphate;

[0061] The protective agent content is 1.0%, specifically bisphenol A dielyl ether;

[0062] The chelating agent content is 2.0%, specifically 4-mercaptobenzoic acid;

[0063] The defoaming agent content is 0.5%, specifically N-phenylbenzylhydroxylamine;

[0064] The remainder is water.

[0065] Example 2:

[0066] The accelerator content is 2.0%, specifically... ;

[0067] The wetting agent content is 2.0%, specifically tris(pentafluorophenyl) phosphate;

[0068] The protective agent content is 1.0%, specifically bisphenol A di(2,3-dihydroxypropyl) ether;

[0069] The chelating agent content is 2.0%, specifically 4-mercaptobutyric acid;

[0070] The defoaming agent content is 0.5%, specifically 2,4-dichlorobenzylhydroxylamine;

[0071] The remainder is water.

[0072] Example 3:

[0073] The accelerator content is 2.0%, specifically... ;

[0074] The wetting agent content is 2.0%, specifically bis(2-(perfluorooctyl)ethyl) phosphate;

[0075] The protective agent content is 1.0%, specifically bisphenol A diglycidyl ether;

[0076] The chelating agent content is 2.0%, specifically 2-mercaptobenzimidazole carboxylic acid;

[0077] The defoaming agent content is 0.5%, specifically N-benzyl-N-hydroxyacetamide;

[0078] The remainder is water.

[0079] Example 4:

[0080] The accelerator content is 1.0%, specifically... ;

[0081] The wetting agent content is 1.0%, specifically tetramethylfluorourea hexafluorophosphate;

[0082] The protective agent content is 0.5%, specifically bisphenol A dielyl ether;

[0083] The chelating agent content is 1.5%, specifically 4-mercaptobenzoic acid;

[0084] The defoaming agent content is 0.2%, specifically N-phenylbenzylhydroxylamine;

[0085] The remainder is water.

[0086] Example 5:

[0087] The accelerator content is 3.0%, specifically... ;

[0088] The wetting agent content is 3.0%, specifically tetramethylfluorourea hexafluorophosphate;

[0089] The protective agent content is 2.0%, specifically bisphenol A dielyl ether;

[0090] The chelating agent content is 3.5%, specifically 4-mercaptobenzoic acid;

[0091] The defoaming agent content is 1.0%, specifically N-phenylbenzylhydroxylamine;

[0092] The remainder is water.

[0093] Based on Example 1, developing solutions for Comparative Examples 1-12 were prepared.

[0094] Comparative Example 1

[0095] The only difference between Comparative Example 1 and Example 1 is that the components do not contain an accelerator.

[0096] Comparative Example 2

[0097] The only difference between Comparative Example 2 and Example 1 is that the components do not contain a wetting agent.

[0098] Comparative Example 3

[0099] The only difference between Comparative Example 3 and Example 1 is that the components do not contain a protective agent.

[0100] Comparative Example 4

[0101] The only difference between Comparative Example 4 and Example 1 is that the components do not contain chelating agents.

[0102] Comparative Example 5

[0103] The only difference between Comparative Example 5 and Example 1 is that the components do not contain defoaming agents.

[0104] Comparative Example 6

[0105] The only difference between Comparative Example 6 and Example 1 is that the concentration of the accelerator in the component is 6.0%.

[0106] Comparative Example 7

[0107] The only difference between Comparative Example 7 and Example 1 is that the concentration of wetting agent in the components is 6.0%.

[0108] Comparative Example 8

[0109] The only difference between Comparative Example 8 and Example 1 is that the concentration of the protective agent in the component is 4.0%.

[0110] Comparative Example 9

[0111] The only difference between Comparative Example 9 and Example 1 is that the concentration of the chelating agent in the component is 7.0%.

[0112] Comparative Example 10

[0113] The only difference between Comparative Example 10 and Example 1 is that the concentration of the defoamer in the component is 2.0%.

[0114] Comparative Example 11

[0115] Compared with Example 1, the only difference in Comparative Example 11 is that the degree of polymerization of the accelerator n=1, as shown in the following formula (5); that is, in the preparation method of the accelerator in Comparative Example 11, 0.4 mol of 2,5-di-tert-pentylhydroquinone and 0.8 mol of ethylene oxide are used, and the molar ratio of the two is 1:2.

[0116] (5).

[0117] Comparative Example 12

[0118] Compared with Example 1, the only difference in Comparative Example 12 is that the degree of polymerization of the accelerator n=5, as shown in the following formula (6); that is, in the preparation method of the accelerator in Comparative Example 11, 0.4 mol of 2,5-di-tert-pentylhydroquinone and 4.0 mol of ethylene oxide are used, and the molar ratio of the two is 1:10.

[0119] (6).

[0120] Comparative Example 13

[0121] Comparative Example 13 is a developer additive disclosed in prior art CN113504715B. Specifically, its components include: 4% diethylenetriaminepentaacetic acid, 600 ppm ethylene glycol, 400 ppm oxalic acid, and the balance being water.

[0122] The developer additives of the above examples / comparative examples were tested for foaming performance, developing performance, stability performance, and compatibility performance. The specific testing methods are as follows:

[0123] 1) Foam performance: The developer additive from the examples / comparative examples was added to tap water to prepare a 0.6% concentration solution; the test was conducted using an RM-2 digital display Roche foam analyzer at a temperature of 25℃. Ventilation or vibration was avoided during the test to prevent it from affecting foam stability. The initial foam height (unit: mm, denoted as H0) and the time it took for the foam to deflate to half its height (t) were recorded. 1 / 2 Each sample should be tested at least three times in parallel, and the average value should be taken.

[0124] 2) Development performance: The development additives of the examples / comparative examples were used to develop IC substrates with a line width / spacing of 10μm according to the following development process; the ability to clearly develop patterns was observed, and the proportion of dry film remaining on the circuit board surface after development was tested using an SU1510 scanning electron microscope, i.e., the development residue rate. The development residue rate should be ≤0.5%.

[0125] The developing process is as follows: degreasing → water washing → drying → film application → exposure → developing → water washing → etching → water washing → film removal → water washing → drying; the developing additives in the examples / comparative examples are used in the developing process, which is divided into three processing stages: pre-immersion stage → developing stage 1 → developing stage 2.

[0126] The process parameters for the pre-impregnation section are as follows: the solution composition in the pre-impregnation tank is 0.5% sodium carbonate and the remainder is water; this section is an immersion type, the pre-impregnation temperature is 25±1℃, the length of the pre-impregnation section is 0.5m, and the linear velocity is 2.0±0.2m / min.

[0127] The process parameters for the first developing stage are as follows: this stage is a spray-type stage; the developing solution in the developing tank consists of 1.2% sodium carbonate, 0.6% developing additive prepared in the examples / comparative examples, and the remainder is tap water; the developing temperature is 25±1℃; the length of the first developing stage is 1.0m; the linear velocity is 2.0±0.2m / min; and the pressure is 1.5±0.5kg / cm. 2 ;

[0128] The process parameters for the second developing stage are as follows: this stage is a spray-type stage; the developing solution in the developing tank consists of 0.6% sodium carbonate, 0.3% developing additive prepared in the examples / comparative examples, and the remainder is tap water; the developing temperature is 25±1℃, the developing stage length is 1.0m, the linear velocity is 2.0±0.2m / min, and the pressure is 1.0±0.5 kg / cm². 2 ;

[0129] 3) Stability: Firstly, storage stability was tested. The developer additive was stored at 40°C for 7 days, and the changes in surface tension were observed on the first and seventh days. The surface tension was tested using the capillary rise method. Specifically, a clean capillary was vertically inserted into the developer additive of the example / comparative example. Due to surface tension, the solution rose a certain height within the capillary. Based on parameters such as capillary radius, solution density, gravitational acceleration, and the height the solution rose within the capillary, the surface tension of the solution could be calculated using relevant formulas. The calculation formula is as follows: Where γ is the surface tension; r is the capillary radius; h is the height the solution rises in the capillary; ρ is the density of the solution; g is the acceleration due to gravity; and θ is the contact angle.

[0130] 4) Compatibility performance: Immerse the developing additives of the examples / comparative examples with IC substrate materials and observe whether the dry film swells or the metal surface corrodes; if there are no such phenomena, the test result is excellent; if the above phenomena occur, the test result is poor.

[0131] The performance test results of Examples 1-5 and Comparative Examples 1-13 are shown in Table 1:

[0132] Table 1 Performance Test Results

[0133]

[0134] Example 1: The developed pattern observed under an optical microscope after development is as follows. Figure 1 As shown; Example 4: The developed pattern observed under an optical microscope after development is shown in the figure. Figure 2 As shown; the developed pattern observed under an optical microscope after development in Comparative Example 12 is as follows. Figure 3 As shown; the developed pattern observed under an optical microscope after development in Comparative Example 13 is as follows. Figure 4 As shown.

[0135] As can be seen from the experimental data of Examples 1-5 in Table 1, the low-foaming developer additive of the present invention for IC substrate development has a foam height of 2.5-2.9 mm and a foam elimination time of 2.0-2.2 s; the development residue rate of circuit boards with a line width / spacing of 10 μm is 0.02-0.06%; the surface tension of the product remains unchanged on the first and seventh days, demonstrating excellent stability; when the surface of the circuit board is soaked with the developer additive of the present invention, the dry film does not swell and the metal surface does not corrode, demonstrating excellent compatibility. This indicates that the low-foaming developer additive of the present invention for IC substrate development has advantages such as low foaming, rapid defoaming, thorough development, stability, durability, and wide compatibility. It can be applied to the development process of IC substrates with a line width / spacing of 10 μm, producing clear and complete patterns after development with a low development residue rate, which is beneficial for high-precision IC substrate forming. The product exhibits good stability and excellent compatibility with dry film and metal surfaces, reducing the IC substrate development defect rate and improving manufacturing efficiency.

[0136] The difference between Comparative Examples 1-5 and Example 1 is that they lacked individual components of accelerator, wetting agent, protectant, chelating agent, and defoamer, respectively. Test results showed that the absence of accelerator and defoamer significantly affected foam height, residual development rate, and product surface tension, indicating that accelerator and defoamer components help accelerate development, achieve finer development, and provide low surface tension. The absence of wetting agent, protectant, and chelating agent slightly reduced foam height, residual development rate, and product surface tension in the developing additive, resulting in poorer product compatibility, indicating that these three types of components all play a role in the developing additive. Therefore, the excellent performance of the low-foam developing additive for IC substrate development of this invention is the result of the interaction of its components; the absence of any one component will affect the product's performance.

[0137] The difference between Comparative Examples 6-10 and Example 1 is that the concentrations of the accelerator, wetting agent, protectant, chelating agent, and antifoaming agent are all higher than the upper limit of the concentration of the present invention. The test results show that, compared with Examples 1-5, excessively high concentrations of the accelerator, wetting agent, protectant, chelating agent, and antifoaming agent will not affect the developing performance, but excessively high concentrations will increase the cost of the solution. Therefore, the concentrations of each component of the developing additive of the present invention should not be too high. Stable developing effect of the solution can be guaranteed within the concentration range defined by the present invention.

[0138] The only difference between Comparative Example 11 and Example 1 is that the degree of polymerization of the accelerator is n=1. The test results of Example 1 and Comparative Example 11 show that the foaming performance, residual development rate, and compatibility of Comparative Example 11 are basically the same as those of Example 1, but the product's stability is relatively poor, and the surface tension is also slightly higher, which can easily lead to poor development if used for too long.

[0139] The only difference between Comparative Example 12 and Example 1 is that the degree of polymerization of the accelerator is n=5. The test results from Example 1 and Comparative Example 12 show that Comparative Example 12 has poor foaming performance, residual development rate, and compatibility, making it difficult to meet the requirements for IC substrate development.

[0140] Comparative Example 13 uses a developer additive from the prior art. The test results are compared with those of Example 1, showing that the low-foaming developer additive of the present invention for IC substrate development has lower foam height, faster defoaming time, lower developer residue, lower surface tension and stability, and better compatibility, and is suitable for IC substrate development processes.

[0141] In summary, this invention provides a low-foaming developer additive for IC substrate development. This product has advantages such as low foaming efficiency, precise development, stability, durability, and wide compatibility. It can be applied to the development process of IC substrates with a line width / spacing of 10μm. After development, the pattern is clear and complete with low residual development rate, which is beneficial for high-precision IC substrate forming. The product has good stability and excellent compatibility with dry film and metal surfaces, which can reduce the IC substrate development defect rate and improve manufacturing efficiency.

[0142] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in the present invention, and these modifications or substitutions should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A low-foaming developer additive for developing IC carriers, characterized in that, Components including the following mass concentrations: Accelerator 1.0-3.0%; Wetting agent 1.0-3.0%; Protectant 0.5-2.0%; Chelating agent 1.5-3.5%; Defoamer 0.2-1.0%; The accelerator has the structure of the following formula (1): （1）； In equation (1), the degree of polymerization n = 2, 3, 4; The wetting agent is selected from one or a mixture of more than one of tetramethylfluorourea hexafluorophosphate, tris(pentafluorophenyl) phosphate, and bis(2-(perfluorooctyl)ethyl) phosphate; The protective agent is selected from one or a mixture of more than one of bisphenol A dielyl ether, bisphenol A di(2,3-dihydroxypropyl) ether, and bisphenol A diglycidyl ether; The chelating agent is selected from one or a mixture of more than one of 4-mercaptobenzoic acid, 4-mercaptobutyric acid, and 2-mercaptobenzimidazole carboxylic acid; The defoaming agent is selected from one or a mixture of more than one of N-phenylbenzylhydroxylamine, 2,4-dichlorobenzylhydroxylamine, and N-benzyl-N-hydroxyacetamide.

2. The low-foaming developer additive for IC carrier development according to claim 1, characterized in that, The preparation method of the accelerator is as follows: First, 2,5-di-tert-pentylhydroquinone, ethylene oxide, acetonitrile, triethylamine, and potassium hydroxide are placed in a high-pressure reactor. After the air in the reactor is vented, the temperature is raised to 80±2℃ and reacted for 45-50 hours. The mixture is then cooled to room temperature and the crude product is collected. The crude product is then subjected to rotary evaporation, dichloromethane solvent extraction, and drying to obtain the accelerator. By adjusting the molar ratio of 2,5-di-tert-pentylhydroquinone and ethylene oxide, accelerators with different degrees of polymerization (n) can be obtained. When the ratio is 1:4, n=2; when the ratio is 1:6, n=3; and when the ratio is 1:8, n=4.

3. The low-foaming developer additive for IC carrier development according to claim 1, characterized in that, It consists of components with the following mass concentrations: Accelerator 1.0-3.0%; Wetting agent 1.0-3.0%; Protectant 0.5-2.0%; Chelating agent 1.5-3.5%; Defoamer 0.2-1.0%; The remainder is water.

4. The method for preparing the low-foaming developer additive for IC carrier development as described in any one of claims 1-3, characterized in that, Weigh out the promoter, wetting agent, protective agent, chelating agent, and defoaming agent according to the required mass concentration, add them to water, and mix evenly at room temperature to obtain a low-foaming developer additive for IC carrier development.

5. A developer, characterized in that, It contains a low-bubbling developer additive for IC carrier development as described in any one of claims 1-3.

6. The developer according to claim 5, characterized in that, It contains 0.3-0.6% by mass of the low-bubbling developer additive for IC carrier development.

7. The developer as described in claim 5 or 6, characterized in that, Developing for IC substrates with 10μm linewidth / spacing.

8. A developing method for the developing process in IC substrate production, characterized in that, The development process includes the following steps in sequence: Development Stage 1 and Development Stage 2: Developing Stage 1: The IC substrate is sprayed with developing solution from developing stage 1. The developing solution from developing stage 1 consists of sodium carbonate with a mass concentration of 1.0-1.5%, low-foaming developing additive for IC substrate development as described in any one of claims 1-3, and the balance being water. The spraying pressure is 1.5 ± 0.5 kg / cm². 2 The spraying time is 30±5s; Developing Stage 2: The IC substrate treated in Developing Stage 1 is sprayed with developing stage 2 developer solution; the developing stage 2 developer solution consists of 0.5-1.0% sodium carbonate (by mass), 0.3-0.4% of the low-foaming developing additive for IC substrate development as described in any one of claims 1-3, and the balance being water, with a spraying pressure of 1.5 ± 0.5 kg / cm². 2 The spraying time is 30±5s.

9. The developing method according to claim 8, characterized in that, Before the development stage, there is a pre-immersion stage: the exposed IC substrate is immersed in the pre-immersion solution for 15±2s; the pre-immersion solution consists of sodium carbonate with a mass concentration of 0.4-0.6% and the remainder water.

10. A developing method, characterized in that, The process includes the following steps in sequence: pre-immersion stage, developing stage 1, and developing stage 2: Pre-immersion stage: The exposed IC substrate is immersed in the pre-immersion solution for 15±2s; the pre-immersion solution consists of 0.5% sodium carbonate and the remainder water. Developing Stage 1: The IC substrate is sprayed with developing solution from developing stage 1. The developing solution from developing stage 1 consists of 1.2% sodium carbonate (by mass), 0.6% of the low-foaming developing additive for IC substrate development as described in any one of claims 1-3, and the remainder water. The spraying pressure is 1.5 ± 0.5 kg / cm². 2 The spraying time is 30±5s; Developing Stage 2: The IC substrate treated in Developing Stage 1 is sprayed with developing stage 2 developer solution; the developing stage 2 developer solution consists of 0.6% sodium carbonate (by mass), 0.3% of the low-foaming developing additive for IC substrate development as described in any one of claims 1-3, and the remainder water, with a spraying pressure of 1.5 ± 0.5 kg / cm². 2 The spraying time is 30±5s.

Images