Photoresist stripping liquid composition and method of making same

Abstract

The present disclosure provides a photoresist stripping liquid composition and a preparation method thereof, and relates to the field of photoresist stripping liquid, and through setting the photoresist stripping liquid composition, the photoresist stripping liquid composition simultaneously comprises a first amine compound and a second amine compound, the first amine compound is used for improving the etching rate of metal and its oxide, the second amine compound is used for assisting in dissolving the photoresist and protecting the metal, the first amine compound and the second amine compound are different in kind, under the synergistic action of the two amine compounds, the photoresist can be removed, the metal oxide and the metal residue on the surface of the copper metal can be removed, the etching rate can be controlled, the process yield of the copper process is greatly improved, and the cost is reduced.

Description

Technical Field

[0001] This disclosure relates to the field of display technology, and in particular to a photoresist stripping liquid composition and its preparation method. Background Technology

[0002] With the rapid development of display technology, copper metal wiring has become the mainstream technology in the display product array substrate due to its core advantages of low resistivity, high electron mobility, and adaptability to high-resolution large-size panels, and has completely replaced traditional aluminum metal wiring.

[0003] In copper fabrication processes, a patterned photoresist mask is formed on the surface of a thin copper film using photoresist. This photoresist mask is then used to pattern the copper film, resulting in a patterned copper conductive structure. Finally, the photoresist mask is removed. A photoresist stripping solution is required for removing the photoresist mask. Summary of the Invention

[0004] The embodiments of this disclosure provide a photoresist stripping liquid composition and a method for preparing the same. The photoresist stripping liquid composition can efficiently strip and remove photoresist masks. In addition, it can also slightly etch copper oxides on the copper surface, thereby improving the yield of copper processing and improving product quality.

[0005] The embodiments of this disclosure adopt the following technical solutions: In a first aspect, this application provides a photoresist stripping liquid composition, which comprises the following components: The ingredients include alcohol ether organic solvents, amide organic solvents, a first amine compound, a second amine compound, and auxiliary additives; the first amine compound is used to improve the etching rate of metals and their oxides, and the second amine compound is used to assist in dissolving the photoresist and protecting the metal; the first amine compound and the second amine compound are of different types.

[0006] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the boiling points of the alcohol ether organic solvent and the amide organic solvent are greater than or equal to 100°C.

[0007] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the first amine compound is an alkanolamine compound, and the second amine compound is a cyclic amine compound.

[0008] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the alkanolamine compound includes at least one of ethanolamine, N-methylethanolamine, and isopropanolamine, and the cyclic amine compound includes at least one of N-hydroxyethylpiperazine and 1-hydroxyethyl-4-methylpiperazine.

[0009] In some photoresist stripping solution compositions provided in the embodiments of this disclosure, the auxiliary additives include metal corrosion inhibitors and nonionic surfactants, wherein the metal corrosion inhibitors include at least one acidic compound and at least one amphoteric compound.

[0010] In some photoresist stripping compositions provided in embodiments of this disclosure, the mass fraction of the acidic compound is less than the mass fraction of the amphoteric compound.

[0011] In some photoresist stripping solution compositions provided in the embodiments of this disclosure, the amphoteric compound includes triazole amphoteric compounds, and the acidic compound includes organic acids.

[0012] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the triazole amphoteric compound includes at least one of methylbenzotriazole and benzotriazole, and the organic acid includes at least one of citric acid and gallic acid.

[0013] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the theoretical cloud point of the nonionic surfactant is greater than or equal to the operating temperature of the photoresist stripping liquid composition.

[0014] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the nonionic surfactant includes at least one of fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, isomeric decayl alcohol polyoxyethylene ether, and isomeric tridecyl alcohol polyoxyethylene ether.

[0015] In some photoresist stripping solution compositions provided in the embodiments of this disclosure, the mass fraction of the alcohol ether organic solvent ranges from 40% to 80%, the mass fraction of the amide organic solvent ranges from 10% to 50%, the mass fraction of the first amine compound ranges from 1% to 10%, the mass fraction of the second amine compound ranges from 1% to 10%, and the mass fraction of the auxiliary additive ranges from 0.1% to 7%.

[0016] In some photoresist stripping solution compositions provided in the embodiments of this disclosure, the mass fraction of the metal corrosion inhibitor ranges from 0.02% to 5%, and the mass fraction of the nonionic surfactant ranges from 0.01% to 2%.

[0017] In some of the photoresist stripping liquid compositions provided in the embodiments of this disclosure, the photoresist stripping liquid composition is used to strip photoresist from a copper metal surface.

[0018] Secondly, embodiments of this disclosure provide a method for preparing a photoresist stripping liquid composition, used to prepare the photoresist stripping liquid composition as described in any one of the first aspects, the method comprising: Mix alcohol ether organic solvents and amide organic solvents in a predetermined mass fraction ratio together and stir until homogeneous; Add the first amine compound and the second amine compound sequentially, and stir until homogeneous; Add the auxiliary additives and stir well; Use it after filtration with a filter cartridge.

[0019] In some methods for preparing photoresist stripping liquid compositions provided in the embodiments of this disclosure, the step of adding auxiliary additives and stirring until homogeneous includes: Add the metal corrosion inhibitor and stir well; Add the nonionic surfactant and stir until well mixed.

[0020] In the embodiments of this disclosure, by setting the photoresist stripping solution composition to simultaneously include a first amine compound and a second amine compound, the first amine compound is used to improve the etching rate of metals and their oxides, and the second amine compound is used to assist in dissolving the photoresist and protecting the metal. The first amine compound and the second amine compound are of different types. Under the synergistic effect of the two amine compounds, it is possible to simultaneously remove photoresist and remove metal oxides and metal residues on the copper metal surface in the copper manufacturing process, and to achieve controllable etching rate, which greatly improves the process yield of copper manufacturing and reduces costs.

[0021] The above description is merely an overview of the technical solution disclosed herein. In order to better understand the technical means of this disclosure and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this disclosure more apparent and understandable, specific embodiments of this disclosure are described below. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of this disclosure or related technologies, the accompanying drawings used in the description of the embodiments or prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this disclosure. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Figure 1 An OM diagram of a copper substrate without photoresist stripping is provided; Figure 2 for Figure 1 The OM image of the copper substrate after being stripped using a photoresist stripping solution composition provided in this disclosure; Figure 3 for Figure 1 The OM image of the copper substrate after being stripped using the photoresist stripping solution composition in Comparative Example DB1 of this disclosure; Figure 4 for Figure 1 The OM image of the copper substrate after being stripped using the photoresist stripping solution composition in Comparative Example DB5 of this disclosure; Figure 5 for Figure 1 The OM image of the copper substrate after being stripped using the photoresist stripping solution composition in the comparative example DB8 of this disclosure. Specific Implementation The technical solutions of the embodiments of this disclosure will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this disclosure, and not all embodiments. Based on the embodiments of this disclosure, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this disclosure.

[0024] With the rapid development of display technology, copper metal wiring has become the mainstream technology in the display product array substrate due to its core advantages of low resistivity, high electron mobility, and adaptability to high-resolution large-size panels, and has completely replaced traditional aluminum metal wiring.

[0025] In copper fabrication processes, a patterned photoresist mask is formed on the surface of a thin copper film using photoresist. This photoresist mask is then used to pattern the copper film, resulting in a patterned copper conductive structure. Finally, the photoresist mask is removed. A photoresist stripping solution is required for removing the photoresist mask.

[0026] In copper fabrication processes, photoresist stripping (removing the photoresist mask) is one of the core steps, and the performance of the photoresist stripping solution directly determines the success or failure of the stripping process. Typically, the requirements for the photoresist stripping solution used in this step are as follows: 1. It can efficiently strip the photoresist on the array substrate and remove metal residues (including but not limited to copper and copper oxides) left on the array substrate by previous processes.

[0027] 2. The corrosion rate of copper is controllable, avoiding excessive corrosion of the copper wiring under the photoresist during the removal of the photoresist mask.

[0028] 3. It can efficiently and continuously peel off photoresist within a certain time period, avoiding the photoresist from being peeled off and re-attaching to the array substrate.

[0029] 4. After removing the photoresist mask, a water washing process is usually performed. In the subsequent water washing process, the photoresist stripping solution and the photoresist residue mixed in the photoresist stripping solution have good compatibility with water, which prevents the photoresist residue from re-adhering to the array substrate in the subsequent water washing process.

[0030] Of course, in addition to the performance requirements mentioned above, the composition of the photoresist stripping solution must also meet the environmental protection requirements in relevant industry regulations.

[0031] The photoresist stripping solutions in related technologies cannot simultaneously meet the above performance requirements and still have the following drawbacks. For example, the etching rate of the photoresist stripping solution on the copper wiring surface of the array substrate cannot be controlled. Either the etching rate is too low, making it difficult to remove metal residues on the copper surface caused by previous processes; or the etching rate is too high, causing excessive corrosion of the copper surface, resulting in inaccurate wiring width dimensions or broken wires. Another example is that the stripped photoresist re-adheres on the surface of the array substrate, forming foreign matter residue. When a gate insulating layer is subsequently formed on the copper metal layer (e.g., the gate layer), the gate insulating layer covers the foreign matter, forming protrusions that reduce flatness. These protrusions are easily detached under external force, causing damage to the gate insulating layer and reducing its insulating effect.

[0032] Based on this, this application provides a photoresist stripping solution composition, which is composed of the following components: The ingredients include alcohol ether organic solvents, amide organic solvents, first amine compounds, second amine compounds, and auxiliary additives; the first amine compounds are used to improve the etching rate of metals and their oxides, and the second amine compounds are used to assist in dissolving the photoresist and protecting the metals; the first amine compounds and the second amine compounds are of different types.

[0033] The aforementioned photoresist can include positive photoresist and negative photoresist. In positive photoresist, the exposed areas are dissolved and removed by the developer, while the unexposed areas remain on the substrate to form a pattern. In contrast to positive photoresist, negative photoresist undergoes cross-linking in the exposed areas and is insoluble in the developer, while the unexposed areas are washed away, resulting in a final pattern that matches the light-shielding area of ​​the mask.

[0034] The main matrix material in both positive and negative photoresists is resin.

[0035] In an exemplary embodiment, alcohol ether organic solvents are a class of amphiphilic solvents that simultaneously contain hydroxyl groups (-OH) and ether bonds (COC). That is, alcohol ether organic solvents are both hydrophilic and lipophilic, exhibiting good solubility in both aqueous and oily substances. For example, on the one hand, alcohol ether organic solvents are miscible with aqueous substances such as water, alkalis, and alcohols; on the other hand, they are miscible with organic phases such as resins, inks, and oils.

[0036] In an exemplary embodiment, alcohol ether organic solvents have a good swelling ability on the resin in the photoresist. Specifically, alcohol ether organic solvents can penetrate into the gaps between resin polymer chain segments, rapidly swell the uncrosslinked photoresist, and weaken the adhesion between the photoresist film and the substrate.

[0037] It should be noted that solubility refers to the ability of a solvent to completely disperse solute molecules / chains to form a homogeneous solution (single phase); swelling ability refers to the ability of a solvent to penetrate into a polymer network, causing it to expand in volume while maintaining the coexistence of two phases (gel state). The core difference between the two lies in whether or not the overall structure of the solute is destroyed to form a homogeneous phase.

[0038] In an exemplary embodiment, alcohol ether organic solvents have good interfacial wettability and can quickly wet the photoresist, thereby improving the stripping rate.

[0039] In an exemplary embodiment, alcohol ether amphiphilic solvents can simultaneously dissolve the aqueous system and the photoresist organic polymer, thereby serving as homogeneous stabilizers for the stripping solution system and preventing the photoresist stripping solution from delaminating during the photoresist stripping process.

[0040] For example, alcohol ether organic solvents may include at least one of diethylene glycol monomethyl ether and diethylene glycol monobutyl ether.

[0041] In addition, it should be noted that since alcohol ether organic solvents are hydrophilic, they can help to quickly rinse the photoresist stripping solution composition with pure water in the subsequent water washing process, avoiding the presence of organic solution residue on the substrate, and also avoiding watermarks or spots, thereby improving the yield of subsequent array substrate fabrication.

[0042] Amide-based organic solvents exhibit good solubility for various organic polymers, especially for dense photoresists such as highly cross-linked photoresists and high-temperature carbonized photoresists. In practical applications, photoresists may contain not only resins but also organic dyes and pigments. Amide-based organic solvents demonstrate good solubility for most organic polymers and good compatibility for stripping different types of photoresists.

[0043] For example, amide organic solvents may include methylformamide.

[0044] In addition, in semiconductor fabrication processes, there are often processes such as dry etching, ion implantation, and high-temperature baking. These processes may cause at least part of the photoresist to carbonize or become more dense. Amide organic solvents also have good dissolving ability for this type of photoresist residue after semiconductor processing, which is beneficial for dissolving photoresist such as through holes on copper metal or the edges of complex copper metal patterns, improving the photoresist stripping ability, and avoiding photoresist residue on the copper metal layer.

[0045] In an exemplary embodiment, the content of alcohol ether organic solvents is greater than that of amide organic solvents. This is because alcohol ether organic solvents have good amphiphilic properties and wettability, enabling them to quickly wet, swell, and dissolve most photoresist. Combined with the good solubility of amide organic solvents for densely structured photoresist in localized areas, the combined use of these two methods improves the solubility of the photoresist stripping solution for most types of photoresist, ensuring effective photoresist stripping while expanding its application range.

[0046] It should be noted that both the first and second amine compounds are compounds containing basic active components, unlike the aforementioned amide organic solvents.

[0047] In the photoresist stripping solution composition, both the first and second amine compounds provide alkalinity. Alkaline substances can penetrate the photoresist, accelerating swelling and weakening the adhesion between the photoresist and the substrate. Furthermore, they can synergistically work with the aforementioned solvents to hydrolyze organic polymer groups or disrupt the cross-linking structure of the organic polymers.

[0048] For example, second amine compounds degrade the macromolecules of photoresist into small soluble molecules; and first amine compounds can corrode metals or metal oxides to a certain extent.

[0049] In some of the photoresist stripping solution compositions provided in the embodiments of this disclosure, auxiliary additives include metal corrosion inhibitors and nonionic surfactants.

[0050] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the boiling points of alcohol ether organic solvents and amide organic solvents are greater than or equal to 100°C.

[0051] For example, the difference between the boiling point of alcohol ether organic solvents and amide organic solvents and the operating temperature of the photoresist stripping solution composition in semiconductor processes is greater than or equal to 20°C.

[0052] For example, the difference between the boiling point of alcohol ether organic solvents and amide organic solvents and the operating temperature of the photoresist stripping solution composition in semiconductor processes is greater than or equal to 30°C.

[0053] It should be noted that alcohol ether organic solvents and amide organic solvents with a boiling point greater than or equal to 100℃ can include the following situations: 1. The boiling points of alcohol ether organic solvents and amide organic solvents are each greater than or equal to 100℃; 2. The boiling point of the mixed solvent after mixing alcohol ether organic solvent and amide organic solvent is greater than or equal to 100°C. In this case, the mixed solvent may include at least one solvent with a boiling point greater than or equal to 100°C, and may also include at least one solvent with a boiling point less than or equal to 100°C.

[0054] In practical applications, the photoresist stripping process often involves heating (e.g., heating to the operating temperature of the photoresist stripping solution composition, ~80℃) to improve stripping efficiency. By setting the boiling points of alcohol ether organic solvents and amide organic solvents to be greater than or equal to 100℃, it can be ensured that the photoresist stripping solution composition remains stable during heating, preventing phase separation, and the solvents do not evaporate or are difficult to evaporate, thus preventing a rapid imbalance in the composition ratio of the stripping solution and ensuring the stability of the stripping characteristics of the photoresist stripping solution composition.

[0055] Low-boiling-point solvents evaporate very quickly, which can cause the composition of the stripping fluid to become unbalanced rapidly and can also accumulate a large amount of flammable vapor in a closed environment, posing an explosion risk. High-boiling-point solvents have higher flash points, are more stable in composition during use, and have a wider process window.

[0056] In some of the photoresist stripping liquid compositions provided in the embodiments of this disclosure, the boiling points of alcohol ether organic solvents and amide organic solvents are less than or equal to 250°C.

[0057] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the boiling points of alcohol ether organic solvents and amide organic solvents are less than or equal to 200°C.

[0058] It should be noted that the boiling points of alcohol ether organic solvents and amide organic solvents less than or equal to 250℃ can include the following situations: 1. The boiling points of alcohol ether organic solvents and amide organic solvents are each less than or equal to 250℃; 2. The boiling point of the mixed solvent after mixing alcohol ether organic solvent and amide organic solvent is less than or equal to 250°C. In this case, the mixed solvent may include at least one solvent with a boiling point less than or equal to 250°C, and may also include at least one solvent with a boiling point greater than or equal to 250°C.

[0059] For example, the boiling point of alcohol ether organic solvents is lower than that of amide organic solvents.

[0060] Solvents with excessively high boiling points have high viscosity, which increases the difficulty of subsequent water washing processes and makes it easy to form trace residues on the surface of wafers or substrates. Therefore, alcohol ether organic solvents and amide organic solvents with different boiling points are compounded to balance stripping efficiency and easy cleaning.

[0061] In the photoresist stripping solution composition provided in the embodiments of this disclosure, by setting alcohol ether organic solvents, amide organic solvents, a first amine compound, a second amine compound, and auxiliary additives, the alcohol ether organic solvents have good amphiphilic properties and wettability, and can quickly wet, swell, and dissolve most of the photoresist. Combined with the good dissolving ability of amide organic solvents for densely structured photoresist in local areas, the two are used together. In addition, the photoresist stripping solution composition also includes a first amine compound and a second amine compound. The first amine compound is used to improve the etching rate of metals and their oxides, and the second amine compound is used to assist in dissolving the photoresist and protect the metal. The first amine compound and the second amine compound are of different types. Under the synergistic effect of the two amine compounds, it is possible to simultaneously remove photoresist and remove metal oxides and metal residues on the copper metal surface in the copper process, effectively improving the re-attachment after photoresist removal, effectively removing metal residues, and greatly improving the process yield of the copper process and reducing costs.

[0062] In an exemplary embodiment, the first amine compound is an alcoholic amine compound, and the second amine compound is a cyclic amine compound.

[0063] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the alkanolamine compound includes at least one of ethanolamine, N-methylethanolamine, and isopropanolamine, and the cyclic amine compound includes at least one of N-hydroxyethylpiperazine and 1-hydroxyethyl-4-methylpiperazine.

[0064] For example, the term "alkanolamine compound" refers to at least one of ethanolamine, N-methylethanolamine, and isopropanolamine, meaning that the photoresist stripper composition may include one or more combinations of ethanolamine, N-methylethanolamine, and isopropanolamine. "Multiple combinations" refers to two or more combinations.

[0065] For example, the cyclic amine compound including at least one of N-hydroxyethylpiperazine and 1-hydroxyethyl-4-methylpiperazine means that the photoresist stripper composition may include one or more combinations of N-hydroxyethylpiperazine and 1-hydroxyethyl-4-methylpiperazine.

[0066] The meaning of "at least one" in other places in this specification is the same as here, and will not be repeated here.

[0067] In exemplary embodiments, alkanolamine compounds are organic compounds whose molecules simultaneously contain an amino group (e.g., at least one of -NH2, -NH-, and N-) and a hydroxyl group (-OH). The alkyl carbon chain is simultaneously attached to both the amino and hydroxyl groups, classifying them as hydroxylated alkylamines. The hydroxyl groups in alkanolamine compounds are hydrophilic, while the alkyl carbon chains are lipophilic; they are miscible with water, alcohol ethers, and amide solvents in any proportion, stabilizing the homogeneous stripping solution system and preventing delamination of the photoresist stripping solution composition. Furthermore, the hydroxyl group is an electron-withdrawing group, reducing the electron cloud density of the nitrogen atom, and its basicity is weaker than that of pure straight-chain alkylamines such as ethylenediamine and n-butylamine; the alkaline degradation rate of the photoresist is moderate, and it is less likely to excessively corrode the metal substrate.

[0068] For example, alkanolamine compounds may include at least one of ethanolamine, N-methylethanolamine, and isopropanolamine.

[0069] Ethanolamine has a high boiling point and high complexing ability, which can efficiently swell the polymer cross-linking network in photoresist. At the same time, it can undergo complexation reaction with metal ion impurities to form metal complexes, reducing the residue of impurities on the wafer surface.

[0070] N-methylethanolamine can be used as a pH adjuster to regulate the acidity or alkalinity of the photoresist stripping solution composition.

[0071] Isopropanolamine has a low corrosiveness to metals and can be combined with other alkaline substances to reduce the corrosion of the underlying metal while stripping photoresist.

[0072] It is important to emphasize that the first amine compound (alkanolamine compound) promotes the swelling of photoresist polymers, assisting in the breakage of photoresist polymers into smaller molecules, and can also improve the etching rate of metals and their oxides. The first amine compound (alkanolamine compound) is a basic substance and has a certain degree of etching effect on metals; it can also complex with copper ions to form stable and soluble complexes. By adjusting the ratio of the first amine compound, the second amine compound, and the metal corrosion inhibitor mentioned later, the etching rate of metals and their oxides can be controlled. In this disclosure, the second amine compound is a cyclic amine compound, which may include heterocyclic amines.

[0073] Cyclic amine compounds have a similar alkaline effect to the first type of amine compounds mentioned above. While they have a certain degree of etching effect on metals (weak base, very little corrosion effect), they can also protect the metals.

[0074] The difference between heterocyclic amines and ordinary amines lies in their conjugated cyclic structure. Heterocyclic amines can also undergo coordination complexation reactions with metal ions dispersed in photoresist stripping solutions to form stable metal chelates or complexes. However, due to their conjugated cyclic structure, the adsorption of metal chelates or complexes on metal surfaces is stronger, making them difficult to detach even under high temperature and strong alkaline conditions, thus providing better protection for the metal surface.

[0075] Furthermore, a second amine compound (a cyclic amine compound) is used to assist in dissolving the photoresist.

[0076] Specifically, firstly, cyclic amine compounds, due to their strong polarity, can quickly penetrate into the interior of the cross-linked polymer network of the photoresist, causing the originally dense photoresist layer to swell uniformly and disrupting the adhesion between the photoresist layer and the substrate. Secondly, as a weak base, cyclic amines precisely neutralize the acidic groups in the photoresist, while simultaneously breaking the ester and ether bonds within the photoresist layer, disassembling the large polymer molecules into soluble small molecules. Finally, cyclic amines can work synergistically with solvents to rapidly disperse the disassembled small molecules into the solution, preventing them from re-adsorbing onto the substrate surface, ultimately achieving residue-free photoresist stripping.

[0077] For example, heterocyclic amine compounds may include at least one of N-hydroxyethylpiperazine and 1-hydroxyethyl-4-methylpiperazine.

[0078] In some photoresist stripping solution compositions provided in the embodiments of this disclosure, auxiliary additives include metal corrosion inhibitors and nonionic surfactants, wherein the metal corrosion inhibitors include at least one acidic compound and at least one amphoteric compound.

[0079] For example, metal corrosion inhibitors are used to reduce the etching rate of metals by the aforementioned alcohol ether organic solvents, amide organic solvents, first amine compounds, and second amine compounds, thereby protecting the metals.

[0080] According to the acid-base bron theory, acidic compounds are those that can release protons and exhibit acidity. These substances can undergo neutralization reactions with basic substances, but they usually do not have the ability to bind protons and are unlikely to exhibit basicity at the same time.

[0081] Amphoteric compounds are a special class of compounds whose molecular structure simultaneously possesses acidic sites that can release protons and basic sites that can bind protons. Under different acidic and basic conditions, they can act as proton donors exhibiting acidity or as proton acceptors exhibiting basicity, and can react chemically with strong acids and strong bases respectively. Common amphoteric compounds include amphoteric hydroxides, amino acids, and amphoteric organic molecules.

[0082] Compared to acidic compounds that can only provide protons in one direction, amphoteric compounds possess the dual capabilities of proton supply and acceptance. They have broad-spectrum acid-base compatibility, enabling them to exist stably and function in both acidic and alkaline systems. Relying on the synergistic effect of their own acid-base functional groups, they weaken drastic local pH changes, thereby stabilizing the pH of the photoresist stripping solution composition. This results in a more stable and uniform stripping rate and dissolution process in the photoresist stripping process, avoiding situations where excessive local stripping rates cause corrosion of the metal substrate and incomplete local stripping.

[0083] In the embodiments of this disclosure, the above-mentioned alcohol ether organic solvents, amide organic solvents, first amine compounds, and second amine compounds are all alkaline substances. By setting the metal corrosion inhibitor to include at least one acidic compound and at least one amphoteric compound, the pH value of the photoresist stripping solution composition can be effectively adjusted, thereby avoiding excessive alkalinity and causing excessive corrosion to the metal, and playing a certain degree of protective role for the metal (e.g., copper).

[0084] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the amphoteric compounds include triazole amphoteric compounds, and the acidic compounds include organic acids.

[0085] Amphoteric compounds are compounds that can react with both acids and strong bases to produce salt and water (or salt). Triazole amphoteric compounds are heterocyclic amphoteric organic compounds with three nitrogen atoms on the heterocycle.

[0086] The acidic compound is an organic acid, which is generally weaker than inorganic acids. It can be used to finely adjust the pH value of the photoresist stripping solution composition, thereby further ensuring that the photoresist stripping rate and the metal etching rate of the photoresist stripping solution composition are within an adjustable process range.

[0087] In some photoresist stripping compositions provided in the embodiments of this disclosure, the mass fraction of the acidic compound is less than the mass fraction of the amphoteric compound.

[0088] Based on the previous explanation of acidic and amphoteric compounds, it can be seen that amphoteric compounds are more conducive to stabilizing the overall pH of the photoresist stripping solution, thereby improving process stability. By adding more amphoteric compounds, their advantages can be maximized. However, acidic compounds are also essential, as they can effectively control and adjust alkalinity, avoiding metal corrosion caused by an overall alkaline mixture or excessive alkalinity.

[0089] In the embodiments of this disclosure, by setting the metal corrosion inhibitor to include at least one acidic compound and at least one amphoteric compound, and setting the mass fraction of the acidic compound to be less than the mass fraction of the amphoteric compound, the amphoteric compound has weak acidity and alkalinity, which can reduce the etching rate of the photoresist stripping solution composition on the metal. In addition, the mass fraction of the amphoteric compound allows for more precise control of the pH of the photoresist stripping solution composition, thereby making it easier to control the etching rate of the photoresist and metal in the stripping process, expanding the control range (process margin) of the stripping process, and reducing the difficulty of the stripping process.

[0090] In some of the photoresist stripping liquid compositions provided in the embodiments of this disclosure, the triazole amphoteric compound includes at least one of methylbenzotriazole and benzotriazole, and the organic acid includes at least one of citric acid and gallic acid.

[0091] Both methylbenzotriazole and benzotriazole have good amphoteric properties (acidity and alkalinity), and can appropriately adjust the pH of the photoresist stripping solution composition according to the pH changes of the photoresist stripping solution composition (for example, during the photoresist stripping process, the pH of the photoresist stripping solution composition changes due to changes in temperature and the type of photoresist being stripped). This allows the pH of the photoresist stripping solution composition to be stabilized within an appropriate range.

[0092] Specifically, if the photoresist stripper composition becomes more alkaline (pH increases) during use, triazole amphoteric compounds can dissociate to release H+ ions, which neutralize the alkali and stabilize the pH. If the photoresist stripper composition becomes more acidic (pH decreases) during use, triazole amphoteric compounds can bind to H+ ions, reducing acidity and stabilizing the pH.

[0093] Among them, at least one of citric acid and gallic acid is selected as the organic acid. Since citric acid and gallic acid are relatively weak acidic, they have little impact on pH fluctuations. While finely adjusting the pH, they can improve the pH stability of the photoresist stripping solution composition.

[0094] Organic acids are mild and less corrosive than strong inorganic acids such as sulfuric acid and hydrochloric acid, which can reduce the risk of excessive corrosion of substrates and over-etching of surfaces. In addition, organic acids have good biocompatibility, and their waste liquid is easier to treat, making them more environmentally friendly.

[0095] Citric acid, chemically known as 2-hydroxypropane-1,2,3-tricarboxylic acid, is a widely used polybasic organic acid. Its molecular structure contains three carboxyl groups and one hydroxyl group, exhibiting good water solubility and multi-level dissociation properties. Gallic acid, chemically known as 3,4,5-trihydroxybenzoic acid, is a natural polyphenolic aromatic organic acid. Its molecular structure contains one carboxyl group and three phenolic hydroxyl groups, and it is a typical acidic compound.

[0096] In some photoresist stripping solution compositions provided in the embodiments of this disclosure, nonionic surfactants are a class of surfactants that do not ionize into charged ions in aqueous solutions, thus not introducing additional ionic impurities. Furthermore, nonionic surfactants exhibit extremely high chemical stability, are unaffected by pH value or high concentrations of electrolytes, and can be arbitrarily compounded and mixed with the aforementioned organic solvents. Simultaneously, nonionic surfactants also possess low foaming properties, extremely low irritation, and excellent wetting and penetrating capabilities.

[0097] In the photoresist stripping process, nonionic surfactants can reduce the surface tension of the photoresist stripping solution composition, allowing the composition to quickly wet the photoresist surface and thus accelerating the swelling and dissolution rate of the photoresist. Furthermore, it should be noted that during the photoresist stripping process, the scouring action of the liquid easily generates bubbles and foam. These bubbles and foam on the photoresist surface can easily form protected zones, leading to incomplete removal of localized photoresist and resulting in residue. Adding a small amount of nonionic surfactant can prevent the generation of excessive foam during the stripping process, thereby improving the photoresist residue problem.

[0098] In some of the photoresist stripping compositions provided in the embodiments of this disclosure, the theoretical cloud point of the nonionic surfactant is greater than or equal to the operating temperature of the photoresist stripping composition.

[0099] For example, the photoresist stripping solution composition can be used at a temperature of 50°C to 90°C.

[0100] For example, the operating temperature of the photoresist stripping solution composition can be 60℃~80℃.

[0101] For example, the difference between the theoretical cloud point of the nonionic surfactant and the operating temperature of the photoresist stripper composition is greater than or equal to 2°C.

[0102] For example, the difference between the theoretical cloud point of the nonionic surfactant and the operating temperature of the photoresist stripper composition is greater than or equal to 5°C.

[0103] For example, the difference between the theoretical cloud point of the nonionic surfactant and the operating temperature of the photoresist stripper composition is greater than or equal to 5°C and less than or equal to 30°C.

[0104] For example, the difference between the theoretical cloud point of the nonionic surfactant and the operating temperature of the photoresist stripper composition is greater than or equal to 5°C and less than or equal to 20°C.

[0105] It should be noted that in practical applications, the theoretical cloud point of nonionic surfactants is also affected by other components in the solution in which they are located. For example, a certain amount of organic acid may lower the cloud point. Therefore, in practical applications, the theoretical cloud point of nonionic surfactants may be greater than or equal to the actual cloud point of nonionic surfactants. Thus, when the theoretical cloud point of nonionic surfactants is equal to the operating temperature of the photoresist stripping solution composition, nonionic surfactants can exhibit a uniform transparent state.

[0106] For example, the nonionic surfactant is a polyoxyethylene type nonionic surfactant.

[0107] For polyoxyethylene nonionic surfactants, when heated to a specific temperature, their color suddenly changes from transparent to milky white and they separate into layers. The critical temperature at this point is the cloud point.

[0108] In this disclosure, the theoretical cloud point of the nonionic surfactant is selected to be greater than or equal to the operating temperature of the photoresist stripper composition. This prevents the nonionic surfactant from delaminating during use, improves the dispersion stability of each component in the photoresist stripper composition, and ensures that the component concentration of the photoresist stripper composition immersed in different locations on the substrate is as consistent as possible, thereby improving the uniformity of stripping and dissolution of the photoresist stripper composition at different locations on the substrate.

[0109] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the nonionic surfactant includes at least one of fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, isomeric decayl alcohol polyoxyethylene ether, and isomeric tridecyl alcohol polyoxyethylene ether.

[0110] It is important to reiterate that nonionic surfactants play an irreplaceable role through their unique interface regulation capabilities. These surfactants significantly reduce the surface tension of the washing solution (in subsequent washing processes), allowing the solution to fully penetrate the interface between the stripped material and the substrate. This effectively wets and removes photoresist fragments and surface residues from the substrate surface, resulting in excellent rinsing performance. Simultaneously, these surfactants also possess good emulsifying and dispersing properties, stably dispersing the stripped photoresist in the solution and preventing agglomeration and re-adhesion under high photoresist load conditions. This ensures the stability of stripping performance when processing multiple batches of substrates continuously. Because polyoxyethylene ether-type nonionic surfactants have good water solubility, they easily desorb from the substrate surface during washing without forming new residues. Furthermore, their excellent tolerance to acids, alkalis, and salts ensures stability in strongly alkaline stripping solutions. They also do not contain environmentally unfriendly components such as alkylphenol polyoxyethylene ethers, offering environmental advantages.

[0111] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the mass fraction of alcohol ether organic solvents ranges from 40% to 80%, the mass fraction of amide organic solvents ranges from 10% to 50%, the mass fraction of the first amine compound ranges from 1% to 10%, the mass fraction of the second amine compound ranges from 1% to 10%, and the mass fraction of auxiliary additives ranges from 0.1% to 7%.

[0112] In some photoresist stripping liquid compositions provided in the embodiments of this disclosure, the mass fraction of alcohol ether organic solvents ranges from 45% to 75%, the mass fraction of amide organic solvents ranges from 15% to 45%, the mass fraction of the first amine compound ranges from 2% to 9%, the mass fraction of the second amine compound ranges from 2% to 9%, and the mass fraction of auxiliary additives ranges from 0.1% to 5%.

[0113] In some photoresist stripping solution compositions provided in the embodiments of this disclosure, the mass fraction of alcohol ether organic solvents ranges from 45% to 70%, the mass fraction of amide organic solvents ranges from 18% to 40%, the mass fraction of the first amine compound ranges from 3% to 6%, the mass fraction of the second amine compound ranges from 3% to 6%, and the mass fraction of auxiliary additives ranges from 0.5% to 4%.

[0114] For example, the content of alcohol ether organic solvents is greater than the content of amide organic solvents. Since the boiling point of alcohol ether organic solvents is lower than that of amide organic solvents, setting the content of alcohol ether organic solvents to be greater than that of amide organic solvents can effectively lower the overall boiling point of the mixture, avoiding instability in component content due to solvent evaporation during semiconductor processing.

[0115] For example, the contents of both the first and second amine compounds are less than 10% of the total mass fraction of the mixture, but both are greater than the mass fraction of the auxiliary additives. This ensures that the photoresist stripping solution composition is generally alkaline, which is beneficial for photoresist stripping.

[0116] Since auxiliary additives are mainly used to help adjust the acidity or alkalinity or to help adjust the surface activity of the solution, the photoresist stripping solution composition must be alkaline as a whole to effectively strip the photoresist and ensure the normal progress of the stripping process. Therefore, the mass fraction of auxiliary additives is less than the content of the first amine compound and the second amine compound.

[0117] In some photoresist stripping solution compositions provided in the embodiments of this disclosure, the mass fraction of the metal corrosion inhibitor ranges from 0.02% to 5%, and the mass fraction of the nonionic surfactant ranges from 0.01% to 2%.

[0118] For example, the mass fraction of the metal corrosion inhibitor ranges from 0.03% to 4%, and the mass fraction of the nonionic surfactant ranges from 0.02% to 1%.

[0119] For example, the mass fraction of the metal corrosion inhibitor ranges from 0.04% to 3%, and the mass fraction of the nonionic surfactant ranges from 0.03% to 0.08%.

[0120] Among them, the metal corrosion inhibitor is acidic as a whole and is not suitable for over-alkalinity. It is mainly used to adjust the pH to avoid the metal substrate being corroded by excessive alkalinity.

[0121] Nonionic surfactants can reduce the surface tension of the photoresist stripping solution composition, allowing the photoresist stripping solution composition to quickly wet the photoresist surface. If the content is too high, it is very easy to be adsorbed on the substrate surface, increasing the difficulty of cleaning and causing chemical residues on the metal substrate surface.

[0122] In some of the photoresist stripping liquid compositions provided in the embodiments of this disclosure, the photoresist stripping liquid compositions are used to strip photoresist from a copper metal surface.

[0123] The following provides a specific formulation of the photoresist stripping solution composition and an explanation of its test structure during the stripping process.

[0124] In the table below, A represents alcohol ether organic solvents, A1 represents diethylene glycol monomethyl ether, and A2 represents diethylene glycol monobutyl ether; B represents β-amide organic solvents, B1 represents N-methylformamide, and B2 represents dimethylacetamide; C represents primary amine compounds, C1 represents ethanolamine, C2 represents N-methylethanolamine, and C3 represents isopropanolamine; D represents secondary amine compounds, D1 represents N-hydroxyethylpiperazine, and D2 represents 1-hydroxyethyl-4-methylpiperazine; E represents E-metal corrosion inhibitors, E1 represents methylbenzotriazole, E2 represents citric acid, E3 represents benzotriazole, E4 represents mercaptobenzothiazole, and E5 represents gallic acid; F represents nonionic surfactants, F1 represents fatty alcohol polyoxyethylene ether, F2 represents fatty alcohol polyoxyethylene ether, F3 represents isomeric decaol polyoxyethylene ether, and F4 represents isomeric tridecyl alcohol polyoxyethylene ether.

[0125] Table 1A: Study on the Influence of First Amine Compound C and Second Amine Compound D in the Photoresist Stripping Solution Composition on Photoresist Stripping Performance Testing

[0126] Table 1B: Summary of test performance for each formulation in Table 1A

[0127] Table 1A provides the formulations for five examples S1 to S5, and the formulations for three comparative examples DB1, DB3, and DB4. Table 1B shows the test results for the instantaneous solubility, stripping effect, and Cu etching rate of the photoresist stripping solution compositions for each formulation in Table 1A.

[0128] In all five examples S1-S5, a first amine compound C and a second amine compound D were added simultaneously, while in comparative examples DB1-DB4, only one of the first amine compound C and the second amine compound D was added. As shown in the test results provided in Table 1B, the photoresist stripping solution compositions in Table 1A exhibited good results in terms of immediate solubility, stripping effect, and Cu etching rate. This indicates that the simultaneous addition of the first amine compound C and the second amine compound D, under their synergistic effect, resulted in the photoresist stripping solution compositions achieving the required immediate solubility, stripping effect, and Cu etching rate for the photoresist, and thus passing the performance test. Specifically, for example, Example S1, compared with Comparative Examples DB3 and DB4, forms a control group showing the effect of the first amine compound C. When the first amine compound was absent, the copper etching rate of the stripping solution was significantly reduced. Similarly, Example 1, compared with Comparative Example DB2, forms a control group showing the effect of the second amine compound D. When the second amine compound was absent, the solubility of the stripping solution for the photoresist was significantly reduced, and the stripping effect was also poor. Therefore, it can be seen that the second amine compound can degrade the cross-linked photoresist into soluble small molecule fragments, enhancing its solubility and stripping ability, while also having a certain auxiliary corrosion inhibition effect on copper.

[0129] It should be noted that the method for testing the instantaneous solubility of photoresist in this disclosure is as follows: Add 5 g of dry photoresist to 100 g of the above-mentioned photoresist stripping solution composition heated to 60°C, stir for 10 minutes, and then filter the stripping solution with added photoresist onto filter paper. After filtration, dry the filter paper at 130°C for 3 hours, and record the weight of residual photoresist on the dried filter paper. Further calculate the instantaneous solubility of the photoresist stripping solution composition for photoresist. The above-mentioned dry photoresist is prepared by heating the liquid photoresist composition at 115°C for 5 hours. The greater the instantaneous solubility of the photoresist stripping solution composition for photoresist, the stronger its dissolving ability for photoresist.

[0130] ◎ indicates that the instantaneous solubility of the stripping solution for the photoresist is greater than or equal to 98%; ○ indicates that the instantaneous solubility of the stripping solution in the photoresist is greater than or equal to 95% and less than 98%; ◇This indicates that the instantaneous solubility of the stripping solution in the photoresist is greater than or equal to 90% and less than 95%; ▽ indicates that the instantaneous solubility of the stripping solution for the photoresist is less than 90%. A solubility rating of 98% or higher is considered acceptable.

[0131] In this disclosure, the method for testing the stripping effect of photoresist is as follows: At 60°C, a copper substrate sample containing photoresist was immersed in a photoresist stripping solution prepared according to the formulations of the examples and comparative examples, and agitated for 120 seconds. It was then rinsed with ultrapure water for 1 minute and finally dried with high-purity nitrogen gas to obtain the sample after photoresist stripping. After cleaning, the surface of the sample was observed using an OM (Optical Ranging) instrument to check for any photoresist residue. This test can further evaluate the stripping ability, dissolving ability, and water washing ability of the stripping solution for photoresist.

[0132] ◎ indicates that the substrate surface is very clean; ○ indicates that the substrate surface is relatively clean; ◇ indicates that there is some photoresist residue on the substrate surface; ▽ indicates a large amount of residue on the substrate surface. A very clean substrate surface indicates a satisfactory peeling effect.

[0133] In this disclosure, the method for testing the etching rate of copper by the photoresist stripping solution composition is as follows: Take a 3cm*3cm copper-plated substrate and immerse it in 30mL of a photoresist stripping solution at 60℃. After immersion for 10 minutes, remove the substrate, stir the stripping solution to mix evenly, and send it for ICP testing to determine the copper ion content of the solution after immersion. Calculate the copper etching rate. The copper film decay rate should be controlled within 10-20 Å / min within 30 minutes.

[0134] Specifically, a molybdenum-niobium layer (150Å) and a copper layer (3500Å) were sputtered onto a glass substrate by vapor deposition, and then cut into small test copper-plated substrates of 3cm*3cm in a clean room.

[0135]

[0136] Where v is the etching rate, in Å per minute (min).

[0137] C1 represents the concentration of copper ions in the solution after soaking, in micrograms per liter (μg / L).

[0138] C0 represents the concentration of copper ions in the solution before soaking, expressed in micrograms per liter (μg / L).

[0139] V represents the volume of the etching solution, in liters (L).

[0140] 10 8 is the unit conversion factor from centimeters (cm) to angstroms (Å).

[0141] ρ is the density of copper, a constant, taken as 8.96 g / cm³.

[0142] A 总 This represents the total effective surface area of ​​the copper-plated substrate in contact with the solution.

[0143] t represents the immersion time, unit: minute (min).

[0144] Table 2A: Study on the effect of metal corrosion inhibitor E in photoresist stripping solution composition formula on photoresist stripping performance test

[0145] Table 2B: Summary of test performance corresponding to each formula in Table 2A

[0146] Table 2A provides the formulas of six groups of examples S6 to S11 and the formulas of six groups of comparative examples DB5 to DB10. Table 2B shows the test results of instantaneous solubility, stripping effect and Cu etching rate of the photoresist stripping solution compositions of each formula in Table 2A.

[0147] In the six groups of examples S6 to S11, two types of metal corrosion inhibitors are added simultaneously; while in comparative examples DB5 to DB10, only a single type of metal corrosion inhibitor is added. According to the test results provided in Table 2B, in examples S6, S9 and S11, by adding two metal corrosion inhibitors simultaneously, matching triazole amphoteric compounds with appropriate organic acid and under the condition of suitable concentration, the instantaneous solubility to photoresist, stripping effect and Cu etching rate of the photoresist stripping solution composition all meet the product application requirements, and the performance test is qualified. However, in comparative examples DB5 to DB10, a single metal corrosion inhibitor is added, and most of the corresponding photoresist stripping solution compositions cannot simultaneously meet the application requirements in terms of the three properties of instantaneous solubility to photoresist, stripping effect and Cu etching rate, resulting in unqualified performance test. Specifically, when only a small amount of triazole-based metal corrosion inhibitor is present, the stripping effect is good, but the metal corrosion rate is difficult to control, and pitting corrosion easily occurs, thereby reducing the yield of subsequent products. When the content of a single corrosion inhibitor is increased, due to the complexation between the corrosion inhibitor, organic alkali and copper, compounds that are difficult to be washed away by water remain on the substrate surface, thereby affecting the stripping effect. The combination of two appropriate corrosion inhibitors can promote and increase solubility, inhibit the deposition of residues, and improve the water washing removal efficiency at the same time.

[0148] Table 3A: Study on the effect of nonionic surfactant F in photoresist stripping solution composition formula on photoresist stripping performance test

[0149] Table 3B: Summary of test performance corresponding to each formula in Table 3A

[0150] Table 3A provides the formulations for four examples S12-S15, and a formulation for comparative example DB11. Table 3B shows the test results for the instantaneous solubility, re-adhesion stripping effect, and Cu etching rate of the photoresist stripping solution compositions for each formulation in Table 2A. Comparing Tables 3A and 3B, it can be seen that the presence of nonionic surfactants can effectively alleviate the re-adhesion phenomenon. The addition of nonionic surfactants can significantly reduce the surface tension of the stripping solution, significantly improve the wettability and penetration of the stripping solution on the photoresist surface, ensure the uniformity of stripping, and at the same time, uniformly disperse the stripped photoresist resin particles in the system, preventing residue agglomeration and re-adsorption and deposition on the substrate surface.

[0151] It should be noted that, in this disclosure, the test method for the photoresist stripping solution composition (hereinafter referred to as stripping solution) on the re-adhesion and stripping effect of photoresist is as follows: Weigh 10g of dry photoresist and add it to 100g of freshly prepared stripping solution, stir well, and set aside. At 60℃, immerse the copper substrate sample coated with photoresist into the 10wt% photoresist stripping solution prepared in the above examples and comparative examples, and agitate to peel off for 120s. Then rinse with ultrapure water for 1min, and finally dry with high-purity nitrogen to obtain the sample after photoresist stripping. After cleaning, observe the surface using an OM (Optical Markov Model) to check for photoresist residue. It should be noted that re-adhesion often occurs under high photoresist concentration and high load conditions; undissolved photoresist particles may re-adhere to the substrate surface.

[0152] Figure 1 An OM image of a copper substrate without photoresist stripping is provided, showing that the copper substrate has patterned photoresist. Figure 2 for Figure 1 The OM image of the copper substrate after being stripped using a photoresist stripping solution composition provided in this disclosure shows that the stripping effect is excellent. Figure 3 for Figure 1 The OM image of the copper substrate after being stripped using the photoresist stripping solution composition in Comparative Example DB1 of this disclosure. Figure 4 for Figure 1 The OM image of the copper substrate after being stripped using the photoresist stripping solution composition in Comparative Example DB5 of this disclosure. Figure 5 for Figure 1 The OM image shows the copper substrate after being stripped using the photoresist stripping solution composition in Comparative Example DB8 of this disclosure. As can be seen, Figures 3-5 The peeling effect was not good.

[0153] Based on the test results of the instant solubility, stripping effect, re-adhesion stripping effect and Cu etching rate of the aforementioned photoresist stripping liquid compositions and combined with OM images, it can be seen that the photoresist stripping liquid compositions provided in this disclosure have good solubility for photoresist, good stripping effect, and good stripping effect for photoresist residues re-adheded to the substrate, and the Cu etching rate is within a controllable range.

[0154] Embodiments of this disclosure provide a method for preparing a photoresist stripping solution composition, used to prepare a photoresist stripping solution composition as described in any of the preceding claims, the method comprising: S1. Mix the alcohol ether organic solvent and amide organic solvent in a preset mass fraction ratio together and stir until homogeneous; S2. Add the first amine compound and the second amine compound in sequence, and stir until homogeneous; S3. Add auxiliary additives and stir well; S4. Use the filter cartridge for filtration and then set aside.

[0155] In some methods for preparing photoresist stripping solution compositions provided in the embodiments of this disclosure, step S3, adding auxiliary additives and stirring until homogeneous, includes: S31. Add metal corrosion inhibitor and stir well; S32. Add nonionic surfactant and stir until homogeneous.

[0156] Specifically, in practical applications, the photoresist stripping solution composition can be prepared using the following method: Step 1: Weigh out each component in the specified amounts; Step 2: After mixing the alcohol ether organic solvent and the amide organic solvent evenly, add the first amine compound and the second amine compound in sequence, and stir at room temperature for 5 minutes; Step 3: After stirring evenly, add the metal corrosion inhibitor (if it is a compound of multiple metal corrosion inhibitors, add the acid corrosion inhibitor last), stir at room temperature for 5 minutes to allow it to dissolve completely, and finally add the surfactant until it is completely dissolved and the solution is clear and transparent.

[0157] Step 4: The photoresist stripping solution composition is filtered sequentially using 0.2μm and 0.1μm filter elements to remove minute foreign matter that may be introduced during the preparation process due to factors such as raw material purity and environmental cleanliness. Since the photoresist stripping solution composition is used in semiconductor fabrication, which requires high cleanliness, a filtration step is added.

[0158] In the embodiments of this disclosure, by setting the photoresist stripping solution composition to simultaneously include a first amine compound and a second amine compound, the first amine compound is used to improve the etching rate of metals and their oxides, and the second amine compound is used to assist in dissolving the photoresist and protecting the metal. The first amine compound and the second amine compound are of different types. Under the synergistic effect of the two amine compounds, it is possible to simultaneously remove photoresist and remove metal oxides and metal residues on the copper metal surface in the copper manufacturing process, and to achieve controllable etching rate, which greatly improves the process yield of copper manufacturing and reduces costs.

[0159] In the embodiments of this disclosure, the terms "first," "second," "third," and "fourth" are used to distinguish identical or similar items with essentially the same function and effect, solely for the purpose of clearly describing the technical solutions of the embodiments of this disclosure, and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated.

[0160] In the embodiments of this disclosure, the terms "upper" and "lower" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this disclosure and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting this disclosure.

[0161] In the description of this specification, the terms "one embodiment," "some embodiments," "exemplary embodiment," "example," "specific example," or "some examples," etc., are intended to indicate that a particular feature, structure, material, or characteristic associated with that embodiment or example is included in at least one embodiment or example of this disclosure. The illustrative representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics mentioned may be included in any suitable manner in any one or more embodiments or examples.

[0162] In embodiments of this disclosure, "a plurality of" means two or more, and "at least one" means one or more, unless otherwise expressly and specifically defined.

[0163] As used in this disclosure, "parallel," "perpendicular," "equal," and "flush" include the described situation and situations that are similar to the described situation, within an acceptable deviation range, which is determined by those skilled in the art taking into account the measurement under discussion and the error associated with the measurement of a particular quantity (i.e., the limitations of the measurement system). For example, "parallel" includes absolute parallelism and approximate parallelism, wherein an acceptable deviation range for approximate parallelism may be, for example, within 10° or 5°; "perpendicular" includes absolute perpendicularity and approximate perpendicularity, wherein an acceptable deviation range for approximate perpendicularity may also be, for example, within 10° or 5°. "Equal" includes absolute equality and approximate equality, wherein an acceptable deviation range for approximate equality may be, for example, a difference between the two equals being less than or equal to 5% of either one. "Flush" includes absolute flush and approximate flush, wherein an acceptable deviation range for approximate flush may be, for example, a distance between the flushes being less than or equal to 5% of either one's dimension.

[0164] Unless the context otherwise requires, throughout the specification and claims, the term "comprising" is interpreted as open and encompassing, that is, "including, but not limited to".

[0165] In this specification, "electrical connection" and "coupling" include situations where components are connected together by elements that have some electrical function. There are no particular limitations on what constitutes an "electrical function," as long as it allows for the transmission and reception of electrical signals between the connected components. Examples of "electrical functions" include not only electrodes and wiring, but also switching elements such as transistors, resistors, inductors, capacitors, and other components with various functions.

[0166] In this specification, the term "same-layer arrangement" refers to a structure formed by patterning two (or more) structures through the same patterning process, and their materials may be the same or different. For example, the precursors forming multiple structures in a same-layer arrangement may be made of the same material, while the final materials may be the same or different.

[0167] It should be understood that when a layer or element is referred to as being on another layer or substrate, it can mean that the layer or element is directly on the other layer or substrate, or that there is an intermediate layer between the layer or element and the other layer or substrate.

[0168] "At least one of A, B and C" has the same meaning as "at least one of A, B or C", both including the following combinations of A, B and C: only A, only B, only C, combinations of A and B, combinations of A and C, combinations of B and C, and combinations of A, B and C.

[0169] "A and / or B" includes the following three combinations: A only, B only, and a combination of A and B.

[0170] The above description is merely a specific embodiment of this disclosure, but the scope of protection of this disclosure is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this disclosure should be included within the scope of protection of this disclosure. Therefore, the scope of protection of this disclosure should be determined by the scope of the claims.

Claims

1. A photoresist stripping solution composition, characterized in that, The photoresist stripping solution composition comprises the following components: The ingredients include alcohol ether organic solvents, amide organic solvents, a first amine compound, a second amine compound, and auxiliary additives; the first amine compound is used to improve the etching rate of metals and their oxides, and the second amine compound is used to assist in dissolving the photoresist and protecting the metal; the first amine compound and the second amine compound are of different types.

2. The photoresist stripping solution composition according to claim 1, characterized in that, The boiling points of the alcohol ether organic solvents and the amide organic solvents are greater than or equal to 100°C.

3. The photoresist stripping solution composition according to claim 1, characterized in that, The first amine compound is an alcoholic amine compound, and the second amine compound is a cyclic amine compound.

4. The photoresist stripping solution composition according to claim 3, characterized in that, The alkanolamine compounds include at least one of ethanolamine, N-methylethanolamine, and isopropanolamine, and the cyclic amine compounds include at least one of N-hydroxyethylpiperazine and 1-hydroxyethyl-4-methylpiperazine.

5. The photoresist stripping solution composition according to claim 3, characterized in that, The auxiliary additives include metal corrosion inhibitors and nonionic surfactants, wherein the metal corrosion inhibitors include at least one acidic compound and at least one amphoteric compound.

6. The photoresist stripping solution composition according to claim 5, characterized in that, In the photoresist stripping solution composition, the mass fraction of the acidic compound is less than the mass fraction of the amphoteric compound.

7. The photoresist stripping solution composition according to claim 5, characterized in that, The amphoteric compounds include triazole amphoteric compounds, and the acidic compounds include organic acids.

8. The photoresist stripping solution composition according to claim 7, characterized in that, The triazole amphoteric compound includes at least one of methylbenzotriazole and benzotriazole, and the organic acid includes at least one of citric acid and gallic acid.

9. The photoresist stripping solution composition according to claim 5, characterized in that, The theoretical cloud point of the nonionic surfactant is greater than or equal to the operating temperature of the photoresist stripper composition.

10. The photoresist stripping solution composition according to claim 9, characterized in that, The nonionic surfactant includes at least one of fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, isomeric decayl alcohol polyoxyethylene ether, and isomeric tridecyl alcohol polyoxyethylene ether.

11. The photoresist stripping solution composition according to any one of claims 5 to 10, characterized in that, The mass fraction of the alcohol ether organic solvent ranges from 40% to 80%, the mass fraction of the amide organic solvent ranges from 10% to 50%, the mass fraction of the first amine compound ranges from 1% to 10%, the mass fraction of the second amine compound ranges from 1% to 10%, and the mass fraction of the auxiliary additive ranges from 0.1% to 7%.

12. The photoresist stripping solution composition according to claim 11, characterized in that, The mass fraction of the metal corrosion inhibitor ranges from 0.02% to 5%, and the mass fraction of the nonionic surfactant ranges from 0.01% to 2%.

13. The photoresist stripping solution composition according to any one of claims 1 to 10, 12, characterized in that, The photoresist stripping solution composition is used to strip photoresist from the surface of metallic copper.

14. A method for preparing a photoresist stripping solution composition, characterized in that, The method for preparing the photoresist stripping solution composition as described in any one of claims 1 to 13 comprises: Mix alcohol ether organic solvents and amide organic solvents in a predetermined mass fraction ratio together and stir until homogeneous; Add the first amine compound and the second amine compound sequentially, and stir until homogeneous; Add the auxiliary additives and stir well; Use it after filtration with a filter cartridge.

15. The method for preparing the photoresist stripping solution composition according to claim 14, characterized in that, The addition of auxiliary additives and stirring until homogeneous includes: Add the metal corrosion inhibitor and stir well; Add the nonionic surfactant and stir until well mixed.

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