Composition for Cleaning During CMP Processes of TGV Structures and Method Thereof

Abstract

The present invention relates to a cleaning composition and a cleaning method for a CMP process performed during the manufacturing process of a glass substrate-based Through Glass Via (TGV) structure. The cleaning composition comprises a quaternary ammonium salt, an alkanolamine, a glycol ether, an azole compound, a surfactant, and water. By including tetramethylammonium hydroxide and choline hydroxide as the quaternary ammonium salt in a specific ratio, the cleaning composition effectively removes polishing particles and organic residues remaining after the CMP process even under high alkaline conditions of pH 12 or higher, while suppressing excessive corrosion of the glass substrate and metal wiring, allowing the cleaning solution to penetrate uniformly into the high aspect ratio via, and simultaneously removing residual contaminants and preventing re-adsorption.

Description

Technology Field

[0001] The present invention relates to a composition and a cleaning method for cleaning between CMP processes of a TGV structure, and more specifically, to a cleaning composition used between Chemical Mechanical Planarization (CMP) processes performed during the formation process of a glass substrate-based TGV (Through Glass Via) structure and a cleaning method using the same. The invention relates to a cleaning technology that improves the reliability and yield of subsequent processes by effectively removing polishing residues, metal residues, slurry components, and contaminants generated during or between CMP processes of a TGV structure including a via structure penetrating a glass substrate. Background Technology

[0003] Recently, semiconductor packaging technology has been evolving toward the application of glass substrate-based Through Glass Via (TGV) structures to achieve high integration, high-speed signal transmission, and thermal stability. The TGV structure is a structure that electrically connects upper and lower circuits through microvias formed on a glass substrate, and offers the advantages of providing superior insulation characteristics, low dielectric loss, and high dimensional stability compared to silicon-based Through Silicon Via (TSV).

[0004] In the manufacturing process of TGV structures, a Chemical Mechanical Planarization (CMP) process is essential for surface planarization following the copper (Cu) electroplating process for via filling. After the CMP process, abrasive slurry particles, metal oxides, and organic residues remain not only on the surface of the TGV but also inside the high aspect ratio vias; these residues cause bonding defects, electrical leakage, and reduced long-term reliability during subsequent electroplating, bonding, and packaging processes. In particular, since the TGV process requires inter-CMP process conditions in which multiple CMP and cleaning processes are repeatedly performed, the chemical stability of the cleaning composition, metal protection properties, and reproducibility in repeated processes have emerged as important technical challenges.

[0005] Conventional post-CMP cleaning technologies (Korean Patent Publication KR 10-2004-0047959 A, US Patent Publication US 2020-0148979 A1, US Patent Publication US 2022-0106542 A1, etc.) have generally applied methods including azole-based corrosion inhibitors to inhibit copper corrosion. However, while such compositions are advantageous in terms of process stability, there were cases where their cleaning power was limited in sufficiently removing abrasive particles and organic contaminants remaining inside microvias. Accordingly, attempts were made to apply high-alkali conditions to improve cleaning power; however, in environments with a pH of 12 or higher, the corrosion rate of the copper plating layer increased rapidly, and the formation of a protective film by azole-based corrosion inhibitors became unstable, making it difficult to simultaneously satisfy cleaning power and metal protection characteristics.

[0006] Furthermore, under strong alkaline conditions, silicate leaching is accelerated in glass substrates, which can lead to chemical damage such as increased surface roughness, reduced optical transmittance, and the occurrence of microdefects. For this reason, the application of high-alkali cleaning compositions in semiconductor manufacturing processes has been limited, and cleaning systems using a single alkaline component (such as TMAH, NaOH, or KOH) have limitations in that it is difficult to simultaneously achieve cleaning power and protect the substrate and metal.

[0007] Meanwhile, conventional cleaning compositions containing surfactants and organic solvents exhibit a certain level of effectiveness in removing surface contaminants, but there was a problem in that surface energy control after cleaning was insufficient, leading to the re-adsorption of contaminant particles. This re-adsorption phenomenon is particularly pronounced inside high aspect ratio TGV vias, and even if it is not clearly observed immediately after cleaning, it may appear as a defect in subsequent processes, potentially lowering process yield.

[0008] In addition, chemical damage can accumulate on the surfaces of copper and glass substrates due to oxidizers, pH adjusters, and various additives contained in the polishing slurry during multiple CMP steps performed in the TGV process. Furthermore, if polishing particles and reaction byproducts remain inside the vias between CMP processes, there is a risk that they may cause physical damage, such as scratches or microdefects, on the copper surface inside the vias during subsequent processes, thereby degrading electrical characteristics and reliability. Therefore, a cleaning technology is required that can effectively remove polishing particles and chemical residues while protecting the copper inside the vias during the inter-CMP step.

[0009] Accordingly, there is a need to develop a new cleaning composition and cleaning method that can be repeatedly applied during the inter-CMP cleaning step of the TGV structure, maintain stable cleaning performance even under high alkaline conditions of pH 12 or higher, suppress corrosion of the copper plating layer, and simultaneously minimize chemical damage to the glass substrate. In addition, the cleaning composition must be able to uniformly penetrate into the interior of high aspect ratio vias to effectively remove residual contaminants, and suppress the re-adsorption of contaminants by controlling surface energy after cleaning. Prior art literature

[0011] Korean Patent KR 10-2004-0047959 A (June 5, 2004) US Patent 2020-0148979 A1 (May 14, 2020) US Patent 2022-0106542 A1 (April 7, 2022) The problem to be solved

[0012] The present invention was created to solve the above-mentioned problem, and aims to provide a cleaning composition applicable to the inter-CMP cleaning step in the manufacturing process of a glass substrate-based Through Glass Via (TGV) structure, which maintains excellent cleaning power even under high alkaline conditions of pH 12 or higher, effectively suppresses corrosion of the copper (Cu) plating layer, and minimizes chemical damage to the glass substrate, and a cleaning method using the same.

[0013] In addition, the present invention aims to provide a cleaning composition and a cleaning method using the same, which allows the cleaning solution to uniformly penetrate into the interior of high aspect ratio TGV vias to effectively remove polishing slurry particles, metal oxides, and organic contaminants, and ensures stable cleaning performance and process reproducibility even under repetitive inter-CMP process conditions.

[0014] In addition, the present invention aims to provide a cleaning composition and a cleaning method using the same that can improve the electrical characteristics and long-term reliability of a TGV structure by controlling surface energy and interface characteristics after cleaning to suppress the re-adsorption of contaminant particles and preventing the occurrence of defects in subsequent electroplating, bonding, and packaging processes. means of solving the problem

[0016] A composition for cleaning during a CMP process of a TGV structure according to one embodiment of the present invention comprises 0.2 to 2 wt% of a quaternary ammonium salt; 1 to 10 wt% of an alkanolamine; 0.5 to 5 wt% of a glycol ether; 0.02 to 0.2 wt% of an azole compound; 0.05 to 0.5 wt% of a surfactant; and the remainder being water; wherein the quaternary ammonium salt comprises tetramethylammonium hydroxide (TMAH) and choline hydroxide (ChOH), and the weight ratio (TMAH:ChOH) of the tetramethylammonium hydroxide and choline hydroxide is 1:4 to 1:9.

[0017] In addition, as one embodiment of the present invention, the azole compound is characterized by including methylimidazole (MeIm) and pyrazole.

[0018] In addition, as one embodiment of the present invention, the azole compound comprises 2-methylimidazole (2-MeIm) and pyrazole, and is characterized in that the weight ratio of 2-methylimidazole and pyrazole (MeIm:Pyrazole) is 1:2 to 1:4.

[0019] In addition, as an embodiment of the present invention, the alkanolamine is characterized by comprising one or more of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 3-amino-1-propanol, 2-amino-1-propanol, N-methylethanolamine, 2-(dimethylamino)ethanol, 2-(ethylamino)ethanol, aminoethylethanolamine, N,N-dimethylisopropanolamine, diglylamine, 2-hydroxyethylamine, 2-hydroxypropylamine, or a mixture thereof.

[0020] In addition, as an embodiment of the present invention, the glycol ether is characterized by comprising one or more of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether, or a mixture thereof.

[0021] In addition, as an embodiment of the present invention, the azole compound is characterized by comprising one or more of imidazole, 1-methylimidazole, 2-methylimidazole, benzimidazole, 2-mercaptobenzimidazole, imidazoline, pyrazole, 1-phenylpyrazole, 3,5-dimethylpyrazole, 1H-1,2,3-triazole, benzotriazole, tolyltriazole, 2-methylbenzotriazole, 1,2,3-triazole-4-carboxylic acid, or a mixture thereof.

[0022] In addition, as one embodiment of the present invention, the surfactant is characterized as a nonionic surfactant having an average added moles of ethylene oxide (EO) of 14.5 to 15.5 and an HLB value of 15.5 to 16.0.

[0023] In addition, a cleaning method between CMP processes of a TGV structure according to another embodiment of the present invention is,

[0024] By applying a cleaning composition according to any one of claims 1 to 8 to a TGV structure, 20 to 40 It is characterized by cleaning by immersion or spraying for 1 to 10 minutes at a temperature of ℃.

[0025] In addition, as an embodiment of the present invention, the cleaning is characterized by being performed in an ultrasonic application environment of 30 to 40 kHz. Effects of the invention

[0027] The composition for cleaning between CMP processes of a TGV structure according to the present invention combines a quaternary ammonium salt including tetramethylammonium hydroxide (TMAH) and choline hydroxide (ChOH), an alkanolamine, a glycol ether, an azole compound, and a surfactant in a specific content range, thereby enabling selective cleaning characteristics for a glass substrate and a copper plating layer even under high alkaline conditions of pH 12 or higher.

[0028] The present invention has technical significance in that it is a compositional system designed interactively, taking into account the special conditions of a TGV structure in which a glass substrate and a copper plating layer coexist in a high-alkali environment, rather than simply including the above components in parallel.

[0029] Generally, under conditions of pH 12 or higher, cleaning power is enhanced, but at the same time, problems arise in which the etching of the glass substrate and the corrosion of the copper plating layer are accelerated. However, in the present invention, the alkaline environment formed by the combination of quaternary ammonium salts provides sufficient cleaning power, while the corrosion reaction on the copper surface is suppressed by the combined action with alkanolamine and azole compounds. In addition, the interfacial environment formed by glycol ether and a surfactant within a specific HLB range effectively detaches abrasive particles and organic contaminants remaining inside the vias and minimizes the reattachment of the detached particles.

[0030] In particular, by using TMAH and ChOH in combination at a specific weight ratio, excessive chemical etching of the glass substrate, which is prone to occur when using a single quaternary ammonium salt, is mitigated, and the reaction rate of the glass surface is stably controlled even in a high-concentration hydroxide ion environment. As a result, fine etching, increased surface roughness, and the occurrence of microcracks during the CMP process and the inter-process cleaning step are significantly suppressed.

[0031] In addition, the composition of the present invention maintains compositional stability under immersion, spray, and ultrasonic application conditions, and simultaneously achieves the effect of increasing physical cleaning power by ultrasound and the function of inhibiting chemical corrosion. Accordingly, the cleaning efficiency inside TGV vias with a high aspect ratio is improved, while material damage is minimized.

[0032] Therefore, the present invention simultaneously secures high alkaline cleaning power and material selectivity, and achieves a balance of glass substrate protection, copper corrosion inhibition, and via internal cleaning, thereby contributing to process stability and yield improvement of the cleaning process between CMP processes of the TGV structure. Specific details for implementing the invention

[0034] Hereinafter, with reference to the attached drawings, a preferred embodiment of a method for preparing an organic solvent dispersion solution of styrene butadiene rubber according to the present invention will be described in detail so that a person skilled in the art to which the present invention pertains can easily practice the present invention.

[0035] In each drawing of the present invention, the sizes or dimensions of the structures are depicted enlarged or reduced compared to the actual size to ensure clarity of the invention, and known components are omitted to reveal characteristic configurations, so the invention is not limited to the drawings.

[0036] In describing the principles of a preferred embodiment of the present invention in detail, if it is determined that a specific description of related known functions or configurations could unnecessarily obscure the essence of the present invention, such detailed description is omitted.

[0037] In addition, the embodiments described in this specification and the configurations illustrated in the drawings are merely the most preferred embodiments of the present invention and do not represent all of the technical ideas of the present invention; therefore, it should be understood that various equivalents and modifications that can replace them may exist at the time of filing this application.

[0038] The present invention relates to a cleaning composition applied to the cleaning of a TGV (Through Glass Via) structure during the CMP process.

[0039] The cleaning composition of the present invention comprises 0.2 to 2 wt% of a quaternary ammonium salt, 1 to 10 wt% of an alkanolamine, 0.5 to 5 wt% of a glycol ether, 0.02 to 0.2 wt% of an azole compound, 0.05 to 0.5 wt% of a surfactant, and the remainder being water, and more preferably comprises 0.5 to 1.5 wt% of a quaternary ammonium salt, 2 to 6 wt% of an alkanolamine, 1 to 3 wt% of a glycol ether, 0.05 to 0.15 wt% of an azole compound, 0.1 to 0.3 wt% of a surfactant, and the remainder being water.

[0040] The above quaternary ammonium salt comprises tetramethylammonium hydroxide (TMAH) and choline hydroxide (ChOH), with a weight ratio of 1:4 to 1:9. TMAH performs the function of effectively decomposing and removing slurry particles and organic residues remaining after the CMP process, while ChOH serves to mitigate excessive corrosion of glass substrates and metal wiring. Within the specific weight ratio range mentioned above, an effect is achieved in which cleaning power and substrate stability are balanced.

[0041] If the content of the above quaternary ammonium salt is less than 0.2 wt%, the cleaning power may not be sufficiently exhibited, and if it exceeds 2 wt%, there is a risk that the aggressiveness against the substrate surface may increase. Therefore, the above range is a range that simultaneously secures cleaning efficiency and substrate protection characteristics.

[0042] The above alkanolamine serves to stabilize metal ions released during the cleaning process and performs the function of maintaining constant cleaning characteristics by buffering the pH of the composition. If the alkanolamine is less than 1 wt%, the metal stabilization effect may not be sufficient, and if it exceeds 10 wt%, the possibility of residue after cleaning may increase.

[0043] The above alkanolamine comprises one or more of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 3-amino-1-propanol, 2-amino-1-propanol, N-methylethanolamine, 2-(dimethylamino)ethanol, 2-(ethylamino)ethanol, aminoethylethanolamine, N,N-dimethylisopropanolamine, diglylamine, 2-hydroxyethylamine, 2-hydroxypropylamine, or mixtures thereof.

[0044] The above glycol ether serves to dissolve organic binders and organic contaminants in the CMP slurry and improves the penetration of the cleaning solution into the TGV. If the amount is less than 0.5 wt%, the effect of removing organic matter may not be sufficiently exhibited, and if it exceeds 5 wt%, the drying performance after cleaning may be reduced.

[0045] The glycol ether comprises one or more of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether, or a mixture thereof.

[0046] The above azole compound selectively adsorbs to the metal surface to form a protective layer, thereby inhibiting metal corrosion during the cleaning process. If the above azole compound is less than 0.02 wt%, the corrosion inhibition effect may be insufficient, and if it exceeds 0.2 wt%, the cleaning efficiency may decrease.

[0047] The above azole compound comprises one or more of imidazole, 1-methylimidazole, 2-methylimidazole, benzimidazole, 2-mercaptobenzimidazole, imidazoline, pyrazole, 1-phenylpyrazole, 3,5-dimethylpyrazole, 1H-1,2,3-triazole, benzotriazole, tolyltriazole, 2-methylbenzotriazole, 1,2,3-triazole-4-carboxylic acid, or mixtures thereof.

[0048] The above surfactant improves the wettability of the cleaning solution, allowing the cleaning solution to reach the interior of the high aspect ratio structure of the TGV uniformly, and serves to prevent the reattachment of removed particles. If the surfactant is less than 0.05 wt%, the wetting effect may not be sufficient, and if it exceeds 0.5 wt%, foaming and reduced rinsing performance may occur.

[0049] The above surfactant is a nonionic surfactant characterized by having an average moles of ethylene oxide (EO) added of 14.5 to 15.5 and an HLB value of 15.5 to 16.0. The above average moles of EO added and HLB ranges are not merely selection ranges, but functional limiting ranges for simultaneously ensuring cleaning performance and surface stability in the high aspect ratio microstructure of the TGV structure.

[0050] Specifically, when the average molar number of added EO is at the level of 15, the surfactant exhibits balanced characteristics that ensure sufficient hydrophilicity without causing excessive foam formation or residue accumulation after cleaning. When the molar number of added EO is lower than the above range, the wettability of the cleaning solution is not sufficiently ensured, and there may be a tendency for the cleaning solution not to penetrate uniformly into deep areas inside the TGV.

[0051] On the other hand, if the molar amount of EO added is excessively high, the water solubility of the surfactant increases excessively, which may result in problems such as residue remaining on the surface after cleaning or reduced rinsability. In addition, when the HLB value is in the range of 15.5 to 16.0, the cleaning solution exhibits the characteristic of simultaneously improving fine particle dispersion stability and wettability.

[0052] Within the above range, the phenomenon of reattachment of removed slurry particles or metal residues is suppressed, and excellent surface cleanliness is maintained after cleaning. In particular, a characteristic effect was confirmed in which the cleaning solution diffuses uniformly inside high aspect ratio TGV vias and residues attached to the inner wall surface are effectively detached.

[0053] That is, the range of an average added moles of EO of 14.5 to 15.5 and an HLB of 15.5 to 16.0 goes beyond a simple range of physical property selection and corresponds to a region where the balance of cleaning power, penetration, inhibition of particle reattachment, and rinsability after cleaning is simultaneously optimized. Accordingly, the limitation of surfactant characteristics as described above in the present invention can be considered a technical configuration for realizing a characteristic and excellent cleaning effect during the cleaning of the TGV structure during the CMP process.

[0054] As such, the composition of the present invention has the characteristic of effectively removing particles and contaminants remaining inside the microstructure of the TGV structure while suppressing damage to the metal wiring and glass substrate by having each component act complementarily.

[0055] Meanwhile, the composition for cleaning between CMP processes of the TGV structure according to the present invention may include methylimidazole (MeIm) and pyrazole as the azole compounds.

[0056] Methylimidazole has an excellent adsorption initiation rate on metal surfaces, and pyrazole contributes to the formation of a more stable protective layer. When used in combination, a uniform and dense protective film is formed on the metal surface, effectively suppressing oxidation and corrosion that may occur during cleaning.

[0057] According to another embodiment, the azole compound comprises 2-methylimidazole and pyrazole, and their weight ratio may be 1:2 to 1:4. In the above ratio range, the balance between the metal surface protection effect and cleaning efficiency is particularly excellent, and if the ratio deviates from the above range, there may be a tendency for either the protection effect or the cleaning efficiency to decrease.

[0058] A cleaning method for a TGV structure during a CMP process according to another embodiment of the present invention comprises applying the cleaning composition to the TGV structure and cleaning by immersion or spraying at a temperature of 20 to 40 ℃ for 1 to 10 minutes.

[0059] In addition, the cleaning can be performed in an environment where ultrasound is applied at 30 to 40 kHz, and when ultrasound is applied, the detachment of particles attached inside the microstructure is promoted, which can further enhance the cleaning effect.

[0061] The present invention will be explained in more detail below through specific embodiments. The following embodiments are merely examples to aid in understanding the present invention and do not limit the scope of the present invention.

[0063] Examples 1 to 25

[0064] As Examples 1 to 25, a cleaning solution was prepared by dissolving a quaternary ammonium salt and an azole compound in each mixing ratio in deionized water with a resistivity of 18 MΩ·cm or higher for 30 minutes, stirring for 100 parts by weight of a cleaning solution composition having the composition according to Table 1 below, and adding an alkanolamine, a glycol ether, and a surfactant and stirring for about 1 hour.

[0065]

[0067] Comparative Examples 1 to 15

[0068] As Comparative Examples 1 to 15, a cleaning solution was prepared by stirring for 30 minutes with respect to 100 parts by weight of a cleaning solution composition having the composition according to Table 2 below, dissolving a quaternary ammonium salt and a corrosion inhibitor in each mixing ratio in deionized water having a resistivity of 18 MΩ·cm or higher, and adding an alkanolamine, a glycol ether, and a surfactant and stirring for about 1 hour.

[0069]

[0071] Experimental Example

[0072] 1. Experiment on the cleaning degree of organic matter inside the hole

[0074] Performance evaluations of the cleaning solutions prepared in Examples 1 to 25 and Comparative Examples 1 to 15 were conducted on a cleaning evaluation of a TGV structure during the CMP process.

[0075] After immersing the above-prepared specimen at a temperature of 25°C for 5 minutes, washing it with ultrapure water and drying it with nitrogen, the cleaning rate of contaminants inside the hole after cleaning (carbon content) compared to before cleaning was checked using an optical microscope and an Energy Dispersive Spectrometer (EDS), and the results were converted into scores according to the grading table in Table 3 below.

[0077] 2. Copper Corrosion Inhibition Experiment

[0078] Performance evaluations of the cleaning solutions prepared in Examples 1 to 25 and Comparative Examples 1 to 15 were conducted, and corrosion rate evaluations were performed on TGV structures during the CMP process, and the results are shown in Tables 4 and 5 below.

[0079] After immersing the above-prepared specimen at a temperature of 25°C for 30 minutes, washing it with ultrapure water and drying it with nitrogen, the TGV Hole Cu corrosion rate (oxygen content) after washing compared to before washing was checked using an optical microscope and an Energy Dispersive Spectrometer (EDS), and the results were converted into scores according to the grading table in Table 3 below.

[0081] 3. Re-adsorption Inhibition Experiment

[0082] The performance of the cleaning solutions prepared in Examples 1 to 25 and Comparative Examples 1 to 15 was evaluated by assessing the re-adsorption rate of polishing particles on a TGV structure during the CMP process, and the results are shown in Tables 4 and 5 below.

[0083] The above-mentioned specimen was immersed in a cleaning solution in which an abrasive was dispersed at a temperature of 25°C for 5 minutes, then cleaned with ultrapure water and dried with nitrogen. Afterward, the number of abrasive particles inside the hole after cleaning was checked using a particle counter compared to before cleaning, and the results were converted into a score according to the grading table in Table 3 below.

[0085] 4. Glass Etching Suppression Experiment

[0086] The performance of the cleaning solutions prepared in Examples 1 to 25 and Comparative Examples 1 to 15 was evaluated for the degree of inhibition of glass etching of the TGV structure during the CMP process, and the results are shown in Tables 4 and 5 below.

[0087] The above-mentioned specimen was immersed in a cleaning solution at a temperature of 25°C for 60 minutes, then washed with ultrapure water and dried with nitrogen. The glass weight (rate of change) after washing was measured relative to before washing, and the results were converted into scores according to the grading table in Table 3 below.

[0088]

[0089]

[0090]

[0091] As described above, as a result of performing examples and comparative examples on the cleaning composition of the present invention, the examples satisfying the compositional range of the present invention generally exhibited excellent cleaning characteristics.

[0092] Specifically, it was confirmed that the composition according to the embodiment of the present invention effectively removed slurry particles, metal residues, and organic contaminants remaining after the CMP process of the TGV structure, while simultaneously maintaining excellent corrosion inhibition of metal wiring and surface stability of the glass substrate. In particular, based on the total score criterion comprehensively evaluating cleaning power, metal stability, and surface cleanliness, the embodiments showed an overall score of 36 or higher, confirming that the composition ensures a balanced balance of each performance element.

[0093] In contrast, the comparative example was composed of a composition that fell outside the compositional range of the present invention or excluded specific components, and showed a tendency for performance degradation in some items, such as cleaning power or metal stability. As a result, the overall evaluation score was found to be less than 30, indicating a significantly lower level of overall performance compared to the example.

[0095] Table 6 below shows the results of comparing changes in cleaning performance according to changes in the TMAH:Chone ratio.

[0096]

[0098] As shown in Table 6 above, when TMAH and ChOH were used in combination in the range of 1:4 to 1:9 (Examples 1, 12, and 13), the overall performance was excellent with a total score of 36 or higher. In particular, an excellent result with a total score of 38 was confirmed in the composition containing TMAH at a level of 0.15 and Choline at a level of 0.85 (Example 1). In this range, cleaning ability, corrosion resistance, re-adsorption inhibition, and glass etching inhibition characteristics were secured in balance.

[0100] On the other hand, when neither TMAH nor ChOH was included, or when only one of them was used alone (Comparative Examples 1 to 3), the overall performance tended to decrease significantly. In particular, when only Choline was included and TMAH was excluded (Comparative Example 2), the cleaning power decreased significantly, and when only TMAH was included and ChOH was excluded (Comparative Example 3), metal stability and re-adsorption inhibition characteristics were not sufficiently secured.

[0101] In addition, when the ratio of the two components was skewed to an extreme (Comparative Examples 4 and 5), the overall score was less than 30, showing significantly lower performance compared to the embodiments of the present invention. This implies that TMAH and ChOH are not merely identical functional components that provide alkalinity, but rather contribute to the cleaning process through different mechanisms of action. It is interpreted that TMAH plays a role in promoting the decomposition and detachment of organic residues and slurry components, while Choline plays a role in ensuring cleaning stability while mitigating aggressiveness toward the substrate surface.

[0102] Therefore, it is determined that when the two components are used in combination at a specific ratio, a synergistic effect is exhibited in which cleaning power and substrate stability are simultaneously optimized. Consequently, the mixing ratio of TMAH and Choline is not an arbitrary choice but a key factor determining overall cleaning performance, and in particular, the best effect is exhibited when the TMAH:Choline ratio is in the range of 1:4 to 1:9.

[0104] Table 7 below shows the results of comparing changes in cleaning performance according to the combination of azole compounds.

[0105]

[0106] As shown in Table 7 above, when comparing cleaning performance with different types of azole compounds under the same basic composition conditions, it was found that using a combination of azole compounds generally resulted in high performance. In particular, the application of 2-methylpyrazole and pyrazole among the azole compounds demonstrated the most excellent overall cleaning characteristics. The composition containing these two compounds showed balanced results in terms of cleaning ability, copper corrosion inhibition, re-adsorption inhibition, and glass etching inhibition, and maintained a high level of performance in the overall evaluation.

[0108] Table 8 below shows the results of comparing the change in cleaning performance according to the weight ratio (2-MeIm:Pyrazole) of the azole compound combination.

[0109]

[0111] As shown in Table 8 above, the weight ratio of 2-MeIm and Pyrazole in the azole compound combination was found to affect cleaning performance. When the weight ratio of 2-MeIm to Pyrazole was in the range of 1:2 to 1:4, perfect scores were recorded in all cleaning-related categories (cleaning degree, corrosion prevention, re-adsorption inhibition, glass etching inhibition), achieving a total score of 40 points. Conversely, when the ratio of 2-MeIm was relatively low or the ratio of Pyrazole fell outside the range, scores decreased in some categories, resulting in a total score of 38 points. Through this, it can be interpreted that maintaining an appropriate weight ratio of 2-MeIm and Pyrazole in the azole compound combination plays an important role in improving cleaning performance.

[0113] Although the present invention has been described above with reference to embodiments illustrated in the attached drawings, this is merely illustrative, and those skilled in the art will understand that various modifications and equivalent alternative embodiments are possible therefrom. Accordingly, the technical scope of protection of the present invention should be determined by the following claims.

Claims

Claim 1 A composition for cleaning between CMP processes of a TGV structure, comprising: 0.2 to 2 wt% of a quaternary ammonium salt; 1 to 10 wt% of an alkanolamine; 0.5 to 5 wt% of a glycol ether; 0.02 to 0.2 wt% of an azole compound; 0.05 to 0.5 wt% of a surfactant; and the remainder being water; wherein the quaternary ammonium salt comprises tetramethylammonium hydroxide (TMAH) and choline hydroxide (ChOH), and the weight ratio (TMAH:ChOH) of the tetramethylammonium hydroxide and choline hydroxide is 1:4 to 1:

9. Claim 2 A composition for cleaning between CMP processes of a TGV structure, characterized in that, in claim 1, the azole compound comprises methylimidazole (MeIm) and pyrazole. Claim 3 A composition for cleaning between CMP processes of a TGV structure, wherein, in claim 1, the azole compound comprises 2-methylimidazole (2-MeIm) and pyrazole, and the weight ratio of 2-methylimidazole and pyrazole (MeIm:Pyrazole) is 1:2 to 1:

4. Claim 4 A composition for cleaning between CMP processes of a TGV structure according to claim 1, wherein the alkanolamine comprises one or more of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 3-amino-1-propanol, 2-amino-1-propanol, N-methylethanolamine, 2-(dimethylamino)ethanol, 2-(ethylamino)ethanol, aminoethylethanolamine, N,N-dimethylisopropanolamine, diglylamine, 2-hydroxyethylamine, 2-hydroxypropylamine, or a mixture thereof. Claim 5 A composition for cleaning during the CMP process of a TGV structure according to claim 1, wherein the glycol ether comprises one or more of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether, or a mixture thereof. Claim 6 A composition for cleaning during the CMP process of a TGV structure according to claim 1, wherein the azole compound comprises one or more of imidazole, 1-methylimidazole, 2-methylimidazole, benzimidazole, 2-mercaptobenzimidazole, imidazoline, pyrazole, 1-phenylpyrazole, 3,5-dimethylpyrazole, 1H-1,2,3-triazole, benzotriazole, tolyltriazole, 2-methylbenzotriazole, 1,2,3-triazole-4-carboxylic acid, or a mixture thereof. Claim 7 A composition for cleaning between CMP processes of a TGV structure, wherein, in claim 1, the surfactant is a nonionic surfactant, characterized in that the average added moles of ethylene oxide (EO) are 14.5 to 15.5 and the HLB value is 15.5 to 16.

0. Claim 8 A cleaning method for a TGV structure during a CMP process, characterized by applying a cleaning composition according to any one of claims 1 to 7 to a TGV structure and cleaning by immersion or spraying at a temperature of 20 to 40 ℃ for 1 to 10 minutes. Claim 9 A cleaning method for a TGV structure during a CMP process, characterized in that, in claim 8, the cleaning is performed in an ultrasonic application environment of 30 to 40 kHz.

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