Through-silicon via copper film chemical mechanical polishing solution and application thereof

Abstract

The application discloses a through silicon via copper film chemical mechanical polishing liquid and application thereof, and the through silicon via copper film chemical mechanical polishing liquid comprises abrasive, oxidizing agent, chelating agent, corrosion inhibitor and water; the mass percentage of the abrasive in the through silicon via copper film chemical mechanical polishing liquid is 0.002-20%, and the abrasive is composed of large-particle-size abrasive and small-particle-size abrasive; and the mass ratio of the large-particle-size abrasive to the small-particle-size abrasive is (1:4)-(3:7). The through silicon via copper film chemical mechanical polishing liquid provided by the application mixes abrasive with two particle sizes in a specific ratio, increases the contact area of the abrasive and the copper film layer in the polishing process, realizes high and adjustable copper film removal rate under lower pressure, and improves local and overall corrosion and reduces the butterfly-shaped depression of copper after polishing by improving the corrosion inhibitor and the butterfly-shaped depression inhibitor while rapidly removing the copper film.

Description

Technical Field

[0001] This application relates to the field of semiconductor devices, and more particularly to a chemical mechanical polishing slurry for through-silicon via copper films and its application. Background Technology

[0002] With the development of CMOS technology, the feature size of devices has gradually shrunk, and the circuit density has become more complex, making design and manufacturing increasingly difficult. Moore's Law is approaching its physical limits. To solve the signal delay problem and meet performance and power consumption requirements, 3D packaging technology, as a continuation of Moore's Law, has gradually developed. 3D packaging involves stacking chips vertically and using through-hole active circuitry to achieve efficient interconnection. Compared with traditional 2D packaging, it has advantages such as small size, low power consumption, and short signal delay, and has been applied to the industrialization processes of memory chips and CIS.

[0003] Fabricating through-silicon vias (TSVs) on the back of chips using complex processes is crucial for achieving three-dimensional chip stacking. The process mainly involves the following steps: 1. Efficient etching to form numerous vias; 2. Filling the vias with dielectric, adhesion, barrier, and metal layers; 3. Removing the covering metal layer using chemical mechanical polishing (CMP) to achieve planarization and circuit continuity. Due to the significant depth of TSVs, the copper plating thickness in TSV processes is much greater than that of copper interconnects in integrated circuits, reaching 2-10 μm, or even tens of micrometers. This places higher demands on the polishing process of the copper film: achieving a high copper removal rate to increase yield, avoiding localized and overall corrosion, and maintaining a relatively low butterfly depression value to provide a suitable process for subsequent barrier layer polishing.

[0004] As 3D packaging technology matures and through-silicon via (TSV) technology gains wider application, downstream manufacturers are placing higher demands on polishing processes, aiming for higher copper film removal rates while maintaining other specifications. However, the design of chemical mechanical polishing slurries often requires the introduction of various corrosion and depression inhibitors, inevitably leading to a decrease in the copper film removal rate.

[0005] Therefore, developing a chemical mechanical polishing slurry for through-silicon via copper films that takes into account multiple performance aspects is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0006] In view of this, this application provides a chemical mechanical polishing slurry for through-silicon via copper films, which can quickly remove the copper film during the polishing process, effectively improve the local and overall corrosion of the metal material, and reduce the butterfly-shaped depressions of the copper after polishing.

[0007] This application provides a chemical mechanical polishing slurry for through-silicon via copper films, comprising: abrasive, oxidant, chelating agent, corrosion inhibitor, and water;

[0008] The abrasive in the through-silicon via (TSV) copper film chemical mechanical polishing slurry has a mass percentage of 0.002-20%, and is composed of large-diameter and small-diameter abrasive particles; the large-diameter abrasive particle has a D... 50 The value is 70nm to 110nm, and the D of the small-particle abrasive is... 50 The value is 30nm to 50nm, and the mass ratio of the large-particle abrasive to the small-particle abrasive is (1:4) to (3:7).

[0009] In some specific implementations, the corrosion inhibitor has the structure of Formula 1;

[0010] ;

[0011] Wherein, R1 is a straight-chain alkyl group from C7 to C17, R2 and R3 are each independently -H, -CH3, -CH2CH3 or -CH2CH2OH, and m is 2 or 3.

[0012] In some specific implementations, the corrosion inhibitor includes one or more of N-(3-aminopropyl)dodecanoamide, N-(3-aminopropyl)octanoamide, octanoamide-propyl dimethyl tertiary amine, decanoamide-propyl dimethyl tertiary amine, N-[2-(2-hydroxyethylamino)ethyl]dodecanoamide, palmitamide-propyl diethylamine, myristamidopropyl dimethylamine, N-[2-(diethylamino)ethyl]stearamide, stearamidopropyl dimethylamine, stearamidoethyl diethylamine, N-octadecanoyl ethylenediamine, or lauramide-propyl dimethylamine.

[0013] In some specific implementations, the abrasive includes one or more of SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3 and their co-formed products, soft abrasives based on organic polymers, and particles with surface modification by silane coupling agents.

[0014] And / or, the D of the large-particle abrasive 50 The value is 80nm to 110nm, and the D of the small-particle abrasive is... 50 The value ranges from 30nm to 50nm;

[0015] And / or, the oxidant includes one or more of the following: inorganic peroxides, persulfides, organic peroxides, hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate, hypobromic acid, hypobromicate, bromic acid, bromate, perbromic acid, perbromicate, hypoiodic acid, hypoiodide, iodic acid, iodate, periodic acid, periodate, chromic acid, chromate, iron salts, copper salts, ferricyanide, or molybdates;

[0016] And / or, the chelating agent includes one or more amino acids and amino acid derivatives;

[0017] And / or, the pH of the through-silicon via copper film chemical mechanical polishing solution is 5-9.

[0018] In some specific implementations, the abrasive includes one or more of SiO2, Al2O3, and CeO2;

[0019] And / or, the oxidant includes one or more of hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, and sodium perchlorate;

[0020] And / or, the chelating agent comprises one or more of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, or iminodiacetic acid;

[0021] And / or, the pH of the through-silicon via copper film chemical mechanical polishing solution is 6-8.

[0022] In some specific implementations, the through-silicon via copper film chemical mechanical polishing slurry further includes a butterfly depression inhibitor, wherein the butterfly depression inhibitor is selected from compounds with structures of formula 2 and / or formula 3;

[0023] ;

[0024] R4 and R5 are each independently a C6 to C12 straight-chain or branched alkyl group, and M is Na, K or NH4.

[0025] In some specific implementations, the butterfly depression inhibitor of Formula 2 includes potassium 7-tetradecyl sulfate, potassium 8-pentadecanyl sulfate, potassium 7-pentadecanyl sulfate, potassium 8-hexadecyl sulfate, potassium 7-hexadecyl sulfate, potassium 9-heptadecyl sulfate, potassium 8-heptadecyl sulfate, potassium 7-heptadecyl sulfate, potassium 9-octadecyl sulfate, potassium 8-octadecyl sulfate, potassium 7-octadecyl sulfate, potassium 10-nonadecanyl sulfate, potassium 9-nonadecanyl sulfate, potassium 8-nonadecanyl sulfate, potassium 7-nonadecanyl sulfate, potassium 10-eicosyl sulfate, potassium 9-eicosyl sulfate, potassium 8-eicosyl sulfate, potassium 11-twentiethyl sulfate, potassium 12-twentiethyl sulfate, potassium 13-twentiethyl sulfate, potassium 14-twentiethyl sulfate, potassium 15-twentiethyl sulfate, potassium 16-twentiethyl sulfate, potassium 17-twentiethyl sulfate, potassium 18-twentiethyl sulfate, potassium 19-twentiethyl sulfate, potassium 10-twentiethyl sulfate, potassium 19-twentiethyl sulfate, potassium 10-twentiethyl sulfate, potassium 19-twentiethyl sulfate, potassium 11-twentiethyl sulfate, potassium 12-twentiethyl sulfate, potassium 13-twentiethyl sulfate, potassium 14-twentiethyl sulfate, potassium 15-twentiethyl sulfate, potassium 16-twentiethyl sulfate, potassium 17-twentiethyl sulfate, potassium 18-twentiethyl sulfate, potassium 19-twentiethyl sulfate, potassium 11-twentiethyl sulfate, potassium 12-twentiethyl sulfate, potassium 13-twentiethyl sulfate, potassium 14-twentiethyl sulfate Alkyl sulfate, 10-monoalkyl sulfate, 9-monoalkyl sulfate, 11-monoalkyl sulfate, 10-monoalkyl sulfate, 12-trialkyl sulfate, 11-trialkyl sulfate, 12-tetraalkyl sulfate, 7-tetradecyl ammonium sulfate, 8-pentadecanyl ammonium sulfate, 7-pentadecanyl ammonium sulfate, 8-hexadecyl ammonium sulfate, 7-hexadecyl ammonium sulfate, 9-heptadecyl ammonium sulfate, 8-heptadecyl ammonium sulfate, 7-heptadecyl ammonium sulfate, 9-octadecyl ammonium sulfate, 8-octadecyl ammonium sulfate, 7-octadecyl ammonium sulfate, 10-nonadecanyl ammonium sulfate, 9-nonadecanyl sulfate Ammonium sulfate, 8-nonadecanoylammonium sulfate, 7-nonadecanoylammonium sulfate, 10-eicosylammonium sulfate, 9-eicosylammonium sulfate, 8-eicosylammonium sulfate, 11-tetraalkylammonium sulfate, 10-tetraalkylammonium sulfate, 9-tetraalkylammonium sulfate, 11-tetraalkylammonium sulfate, 10-tetraalkylammonium sulfate, 12-trialkylammonium sulfate, 11-trialkylammonium sulfate, 12-tetraalkylammonium sulfate, 7-tetraalkylammonium sulfate, 7-tetraalkylammonium sulfate, 8-pentadecanoylammonium sulfate, 7-pentadecanoylammonium sulfate, 8-hexadecylammonium sulfate, 7-hexadecylammonium sulfate, 9-heptadecylammonium sulfate, 8-heptadecylsulfonium sulfate Sodium sulfate, sodium 7-heptadecyl sulfate, sodium 9-octadecyl sulfate, sodium 8-octadecyl sulfate, sodium 7-octadecyl sulfate, sodium 10-nonadecanyl sulfate, sodium 9-nonadecanyl sulfate, sodium 8-nonadecanyl sulfate, sodium 7-nonadecanyl sulfate, sodium 10-eicosyl sulfate, sodium 9-eicosyl sulfate, sodium 8-eicosyl sulfate, sodium 11-tetradecyl sulfate, sodium 10-tetradecyl sulfate, sodium 9-tetradecyl sulfate, sodium 11-tetradecyl sulfate, sodium 10-tetradecyl sulfate, sodium 12-tridecyl sulfate, sodium 11-tetradecyl sulfate, or sodium 12-tetradecyl sulfate;

[0026] The butterfly-shaped depression inhibitors of Formula 3 include potassium 2-hexyl-1-nonyl sulfate, potassium 2-heptyl-1-nonyl sulfate, potassium 2-hexyl-1-decyl sulfate, potassium 2-heptyl-1-decyl sulfate, potassium 2-octyl-1-decyl sulfate, potassium 2-hexyl-1-undecyl sulfate, potassium 2-heptyl-1-undecyl sulfate, potassium 2-octyl-1-undecyl sulfate, potassium 2-hexyl-1-dodecyl sulfate, potassium 2-heptyl-1-dodecyl sulfate, ammonium 2-hexyl-1-nonyl sulfate, ammonium 2-heptyl-1-nonyl sulfate, ammonium 2-hexyl-1-decyl sulfate, ammonium 2-heptyl-1-decyl sulfate, ammonium 2-octyl-1-decyl sulfate. The sodium sulfate is one or more of the following: 2-hexyl-1-undecyl sulfate, 2-heptyl-1-undecyl sulfate, 2-octyl-1-undecyl sulfate, 2-hexyl-1-dodecyl sulfate, 2-heptyl-1-dodecyl sulfate, 2-hexyl-1-nonyl sulfate, 2-heptyl-1-nonyl sulfate, 2-hexyl-1-decyl sulfate, 2-heptyl-1-decyl sulfate, 2-octyl-1-decyl sulfate, 2-hexyl-1-undecyl sulfate, 2-heptyl-1-undecyl sulfate, 2-octyl-1-undecyl sulfate, 2-hexyl-1-dodecyl sulfate, or 2-heptyl-1-dodecyl sulfate.

[0027] In some specific implementations, the mass percentage of the butterfly-shaped depression inhibitor in the polishing slurry is 0.001~1%.

[0028] In some specific implementations, the through-silicon via copper film chemical mechanical polishing slurry further includes one or more of a pH adjuster, a surfactant, and a bactericide.

[0029] In some specific implementations, the abrasive content in the through-silicon via copper film chemical mechanical polishing slurry is 0.02% to 2% by mass.

[0030] And / or, the oxidant has a mass percentage of 0.1% to 10% in the chemical mechanical polishing slurry for through-silicon via copper films;

[0031] And / or, the chelating agent has a mass percentage content of 0.1% to 15% in the chemical mechanical polishing slurry for through-silicon via copper films;

[0032] And / or, the corrosion inhibitor has a mass percentage content of 0.005~1% in the chemical mechanical polishing slurry for through-silicon via copper films.

[0033] This application also provides an application of the above-described through-silicon via copper film chemical mechanical polishing slurry for semiconductor substrates with copper plating, copper wiring, or through-silicon via copper surfaces, comprising: contacting the through-silicon via copper film chemical mechanical polishing slurry with the semiconductor substrate to be polished and performing chemical mechanical polishing treatment; wherein the surface of the semiconductor substrate to be polished comprises at least one copper or at least a portion of a copper-containing surface.

[0034] In some specific implementations, the semiconductor substrate to be polished further includes a barrier layer and / or a dielectric layer, wherein the barrier layer includes one or more of Ta, TaN, Ti, TiN or SiN; and the dielectric layer includes one or more of TEOS, low k or ultra-low k.

[0035] The chemical mechanical polishing slurry for through-silicon via (TSV) copper film polishing provided in this application increases the contact area between the abrasive and the copper film layer during polishing by mixing abrasives of two different particle sizes in a specific ratio. This improves the copper removal rate and achieves a high and adjustable copper film removal rate under relatively low downpressure conditions (the copper removal rate can reach over 38,000 Å / min at a low downpressure of 2 psi), significantly improving production efficiency. By adding a novel corrosion inhibitor, it effectively inhibits local and overall corrosion of the metal material while achieving a high polishing rate (copper corrosion rate reduced to 31 Å / min), thereby improving product yield. By adding a novel butterfly depression inhibitor, it maintains a low butterfly depression (copper butterfly depression value as low as 407 Å) during high-speed copper film removal and further improves corrosion, laying a good foundation for subsequent barrier layer polishing. In addition, this CMP composition also has excellent polishing selectivity, enabling highly selective removal of copper films relative to barrier layers (such as Ta, TaN, Ti, TiN or SiN) and dielectric layers (such as TEOS, low k or ultra-low). Detailed Implementation

[0036] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.

[0037] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.

[0038] It should be understood that the order of steps or the sequence of actions is not important as long as this application remains operational. Furthermore, two or more steps or actions can be performed simultaneously.

[0039] The use of any and all instances or exemplary language such as “e.g.” or “include” in this document is intended merely to better illustrate the application and does not constitute a limitation on the scope of the application. No language in this specification should be construed as indicating that any unclaimed element is essential to the practice of this application.

[0040] Furthermore, the numerical ranges and parameters used to define this application are approximate values, and the relevant values ​​in the specific embodiments have been presented as precisely as possible. However, any numerical value inevitably contains standard deviations due to individual test methods. Therefore, unless otherwise explicitly stated, it should be understood that all ranges, quantities, values, and percentages used in this disclosure are modified with the word "approximately." Here, "approximately" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a specific value or range.

[0041] This application provides a chemical mechanical polishing slurry for through-silicon via copper films, comprising: abrasive, oxidant, chelating agent, corrosion inhibitor, and water;

[0042] The abrasive in the through-silicon via (TSV) copper film chemical mechanical polishing slurry has a mass percentage of 0.002-20%, and is composed of large-diameter and small-diameter abrasive particles; the large-diameter abrasive particle has a D... 50 The value is 70nm to 110nm, and the D of the small-particle abrasive is... 50 The value is 30nm to 50nm, and the mass ratio of the large-particle abrasive to the small-particle abrasive is (1:4) to (3:7).

[0043] In some specific implementations, the abrasive includes, but is not limited to, one or more of the following: SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3, their co-formed products, soft abrasive particles based on organic polymers, or particles surface-modified with silane coupling agents. The soft abrasive particles based on organic polymers include one or more of the following: polyethylene, polytetrafluoroethylene, polyurethane, polyacrylic acid, polymethacrylic acid, polyacrylate, polymethyl methacrylate, polypropylene, polybutadiene, and common polymer abrasives commonly used in chemical mechanical polishing. This application does not have specific requirements for the selection of the abrasive. The abrasive can have different shapes, including spherical, cocoon-shaped, string-shaped, curved, and various other shapes; this application does not have specific requirements for the shape of the abrasive particles.

[0044] In some specific implementations, the mass percentage content of the abrasive can be 0.002%, 0.005%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.1%, 0.5%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 5%, 10%, 15%, 18%, or 20%, preferably 0.02% to 2%. In some specific implementations, the D of the large-diameter abrasive... 50 The value can be 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 105 nm, or 110 nm, preferably 80 nm to 110 nm; the D of the small-particle abrasive... 50 The values ​​can be 30 nm, 35 nm, 40 nm, 45 nm, or 50 nm; the mass ratio of the large-particle abrasive to the small-particle abrasive can be 1:4, 2:7, 3:10, 1:3, 3:8, 2:5, or 3:7.

[0045] The chemical mechanical polishing slurry for through-silicon via (TSV) copper films described in this application includes a corrosion inhibitor. In some specific implementations, the corrosion inhibitor has a structure of Formula 1;

[0046] ;

[0047] Wherein, R1 is a straight-chain alkyl group from C7 to C17 (which can be C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17), R2 and R3 are each independently -H, -CH3, -CH2CH3 or -CH2CH2OH, and m is 2 or 3.

[0048] Formula 1 is an N-acyldiamine compound, with an amide group containing a long-chain alkyl group at one end and an amino group or a substituted amino group at the other end, connected by an ethylene or propylene group. The long-chain alkyl group must have more than 7 carbon atoms but no more than 17 to achieve the desired effect in improving both local and overall corrosion resistance, as excessive chain length leads to an excessive number of carbon atoms and a decrease in corrosion resistance. The corrosion inhibitor of Formula 1 can effectively reduce both local and overall corrosion of copper, maintaining the original metallic luster of the copper surface. During polishing, under shear force, the copper continuously detaches from and re-bonds onto the copper surface in a "dynamic" manner, thus maintaining a high copper removal rate.

[0049] In some specific implementations, the corrosion inhibitor includes, but is not limited to, one or more of N-(3-aminopropyl)dodecanoamide, N-(3-aminopropyl)octanoamide, octanoamide propyl dimethyl tertiary amine, decanoamide propyl dimethyl tertiary amine, N-[2-(2-hydroxyethylamino)ethyl]dodecanoamide, palmitamide propyl diethylamine, myristamidopropyl dimethylamine, N-[2-(diethylamino)ethyl]stearamide, stearamidopropyl dimethylamine, stearamidoethyl diethylamine, N-octadecanoyl ethylenediamine, and lauramide propyl dimethylamine.

[0050] The corrosion inhibitor has a mass percentage content of 0.005% to 1%, and can be 0.005%, 0.01%, 0.02%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.8%, 0.9%, 0.95%, or 1%, preferably 0.01% to 0.5%.

[0051] The chemical mechanical polishing slurry for through-silicon via (TSV) copper films described in this application includes an oxidizing agent. In some specific implementations, the oxidizing agent includes one or more of the following: inorganic peroxides, persulfides, organic peroxides, hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate, hypobromic acid, hypobromite, bromic acid, bromate, perbromic acid, perbromic acid, hypobromite, hypoiodic acid, hypoiodate, iodic acid, iodate, periodic acid, periodate, chromic acid, chromate, iron salts, copper salts, ferricyanide, or molybdates. In some specific implementations, the oxidizing agent includes one or more of the following: hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, and sodium perchlorate. The oxidizing agent is used to oxidize the metallic copper film into a mixture of copper oxides to allow it to react rapidly with the chelating agent. The oxidant has a mass percentage content of 0.1% to 10%, and can be 0.1%, 0.2%, 0.3%, 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.5%, or 10%, preferably 0.5% to 5%.

[0052] The chemical mechanical polishing slurry for through-silicon via (TSV) copper films described in this application includes a chelating agent. In some specific implementations, the chelating agent includes one or more amino acids and amino acid derivatives. In some specific implementations, the chelating agent includes, but is not limited to, one or more of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, or iminodiacetic acid. This application does not have special requirements for the selection of the chelating agent, but glycine is preferred. The mass percentage of the chelating agent is 0.1% to 15%, and can be 0.1%, 0.2%, 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.5%, 10%, or 15%, preferably 0.5% to 10%.

[0053] The chemical mechanical polishing slurry for through-silicon via copper films provided in this application may also include a butterfly-shaped depression inhibitor, wherein the butterfly-shaped depression inhibitor is selected from compounds with structures of formula 2 and / or formula 3;

[0054] ;

[0055] R4 and R5 are each independently a C6 to C12 straight-chain or branched alkyl group, and M is Na, K or NH4.

[0056] When the alkyl chain is too short or too long, the "protective" effect of the selected branched alkyl sulfate on the Cu surface during chemical mechanical polishing is reduced. When the alkyl chain is too short, the hydrophobic part of the molecule fails to effectively isolate the attack of chemicals on the copper film layer, while when the alkyl chain is too long, the adsorption of the molecule on the Cu surface decreases. Both of these factors lead to "incompleteness" of the protective film layer.

[0057] Preferably, the butterfly depression inhibitor of Formula 2 comprises potassium 7-tetradecyl sulfate, potassium 8-pentadecanyl sulfate, potassium 7-pentadecanyl sulfate, potassium 8-hexadecyl sulfate, potassium 7-hexadecyl sulfate, potassium 9-heptadecyl sulfate, potassium 8-heptadecyl sulfate, potassium 7-heptadecyl sulfate, potassium 9-octadecyl sulfate, potassium 8-octadecyl sulfate, potassium 7-octadecyl sulfate, potassium 10-nonadecanyl sulfate, potassium 9-nonadecanyl sulfate, potassium 8-nonadecanyl sulfate, potassium 7-nonadecanyl sulfate, potassium 10-eicosyl sulfate, potassium 9-eicosyl sulfate, potassium 8-eicosyl sulfate, potassium 11-tetradecyl sulfate. Potassium 10-monoalkyl sulfate, potassium 9-monoalkyl sulfate, potassium 11-monoalkyl sulfate, potassium 10-monoalkyl sulfate, potassium 12-monoalkyl sulfate, potassium 11-monoalkyl sulfate, potassium 12-monoalkyl sulfate, ammonium 7-tetradecyl sulfate, ammonium 8-pentadecanyl sulfate, ammonium 7-pentadecanyl sulfate, ammonium 8-hexadecyl sulfate, ammonium 7-hexadecyl sulfate, ammonium 9-heptadecyl sulfate, ammonium 8-heptadecyl sulfate, ammonium 7-heptadecyl sulfate, ammonium 9-octadecyl sulfate, ammonium 8-octadecyl sulfate, ammonium 7-octadecyl sulfate, ammonium 10-nonadecanyl sulfate, ammonium 9-nonadecanyl sulfate, ammonium 8 -Ninedecyl ammonium sulfate, 7-Ninedecyl ammonium sulfate, 10-Eicosyl ammonium sulfate, 9-Eicosyl ammonium sulfate, 8-Eicosyl ammonium sulfate, 11-Tyroalkyl ammonium sulfate, 10-Tyroalkyl ammonium sulfate, 9-Tyroalkyl ammonium sulfate, 11-Tyroalkyl ammonium sulfate, 10-Tyroalkyl ammonium sulfate, 12-Tyroalkyl ammonium sulfate, 11-Tyroalkyl ammonium sulfate, 12-Tyroalkyl ammonium sulfate, 11-Tyroalkyl ammonium sulfate, 12-Tyroalkyl ammonium sulfate, 7-Tetraalkyl ammonium sulfate, 8-Pentadedecyl ammonium sulfate, 7-Pentadedecyl ammonium sulfate, 8-Hexadecyl ammonium sulfate, 7-Hexadecyl ammonium sulfate, 9-Heptadedecyl ammonium sulfate, 8-Heptadedecyl ammonium sulfate Sodium 7-heptadecyl sulfate, sodium 9-octadecyl sulfate, sodium 8-octadecyl sulfate, sodium 7-octadecyl sulfate, sodium 10-nonadecanyl sulfate, sodium 9-nonadecanyl sulfate, sodium 8-nonadecanyl sulfate, sodium 7-nonadecanyl sulfate, sodium 10-eicosyl sulfate, sodium 9-eicosyl sulfate, sodium 8-eicosyl sulfate, sodium 11-tetradecyl sulfate, sodium 10-tetradecyl sulfate, sodium 9-tetradecyl sulfate, sodium 11-tetradecyl sulfate, sodium 10-tetradecyl sulfate, sodium 12-tetradecyl sulfate, sodium 11-tetradecyl sulfate, or sodium 12-tetradecyl sulfate.

[0058] Preferably, the butterfly depression inhibitor of Formula 3 comprises potassium 2-hexyl-1-nonylsulfate, potassium 2-heptyl-1-nonylsulfate, potassium 2-hexyl-1-decylsulfate, potassium 2-heptyl-1-decylsulfate, potassium 2-octyl-1-decylsulfate, potassium 2-hexyl-1-undecylsulfate, potassium 2-heptyl-1-undecylsulfate, potassium 2-octyl-1-undecylsulfate, potassium 2-hexyl-1-dodecylsulfate, potassium 2-heptyl-1-dodecylsulfate, ammonium 2-hexyl-1-nonylsulfate, ammonium 2-heptyl-1-nonylsulfate, ammonium 2-hexyl-1-decylsulfate, ammonium 2-heptyl-1-decylsulfate, ammonium 2-octyl-1-decylsulfate, ammonium 2-hex ...hexyl-1-decylsulfate, ammonium 2-hexyl-1-decylsulfate, ammonium 2-hexyl-1-decylsulfate, ammonium 2-hexyl-1-decylsulfate, ammonium 2 Ammonium, 2-hexyl-1-undecyl ammonium sulfate, 2-heptyl-1-undecyl ammonium sulfate, 2-octyl-1-undecyl ammonium sulfate, 2-hexyl-1-dodecyl ammonium sulfate, 2-heptyl-1-dodecyl ammonium sulfate, 2-hexyl-1-nonyl sulfate, 2-heptyl-1-nonyl sulfate, 2-hexyl-1-decyl sulfate, 2-heptyl-1-decyl sulfate, 2-octyl-1-decyl sulfate, 2-hexyl-1-undecyl sulfate, 2-heptyl-1-undecyl sulfate, 2-octyl-1-undecyl sulfate, 2-hexyl-1-dodecyl sulfate, or 2-heptyl-1-dodecyl sulfate.

[0059] The butterfly-shaped depression inhibitor provided in this application has two C6-C12 hydrophobic alkyl chains, which can isolate the copper film layer from chemical attack. It has a superior steric barrier effect compared to straight-chain alkyl sulfates with the same number of carbon atoms, and can synergistically work with corrosion inhibitors to further reduce the copper corrosion rate, thereby improving product yield. Simultaneously, the butterfly-shaped depression inhibitor adsorbs onto the surface of the copper film layer within the trench, protecting it from excessive removal during over-polishing, thus significantly improving the butterfly-shaped depressions after polishing. Because it also adsorbs onto the copper film surface at higher steps, the overall copper film removal rate decreases slightly, but a high and adjustable copper removal rate can still be achieved under relatively low downpressure, ensuring production efficiency.

[0060] In some specific implementations, the butterfly indentation inhibitor can be sodium 7-tetradecyl sulfate. Sodium 8-pentadecanyl sulfate Sodium 7-pentadecanyl sulfate Sodium 8-hexadecyl sulfate Sodium 7-hexadecyl sulfate Sodium 9-heptadecyl sulfate Sodium 8-heptadecyl sulfate Sodium 7-heptadecyl sulfate Sodium 9-octadecyl sulfate Sodium 8-octadecyl sulfate Sodium 7-octadecyl sulfate Sodium 10-nonadecanyl sulfate Sodium 9-nonadecanyl sulfate Sodium 8-nonadecanyl sulfate Sodium 7-nonadecanyl sulfate Sodium 10-eicosyl sulfate Sodium 9-eicosyl sulfate Sodium 8-eicosyl sulfate Sodium 11-tetraalkylsulfate Sodium 10-tetraalkylsulfate Sodium 9-tetraalkyl sulfate Sodium 11-docoalkyl sulfate Sodium 10-docosyl sulfate Sodium 1,2-trialkyl sulfate Sodium 11-trialkyl sulfate Sodium 1,2-tetraalkylsulfate Sodium 2-hexyl-1-nonylsulfate Sodium 2-heptyl-1-nonylsulfate Sodium 2-hexyl-1-decyl sulfate Sodium 2-heptyl-1-decyl sulfate Sodium 2-octyl-1-decyl sulfate Sodium 2-hexyl-1-undecyl sulfate Sodium 2-heptayl-1-undecyl sulfate Sodium 2-octyl-1-undecyl sulfate Sodium 2-hexyl-1-dodecyl sulfate Sodium 2-heptayl-1-dodecyl sulfate In some specific implementations, the butterfly depression inhibitor may also be a potassium or ammonium salt of the aforementioned branched alkyl sulfate, or a mixture thereof.

[0061] Preferably, the mass percentage of the butterfly-shaped depression inhibitor is 0.001% to 1%, and can be 0.001%, 0.005%, 0.01%, 0.02%, 0.05%, 0.1%, 0.15%, 0.2%, 0.3%, 0.5%, 0.8%, or 1%, and is more preferably 0.01% to 0.2%.

[0062] In some specific implementations, the through-silicon via copper film chemical mechanical polishing slurry further includes one or more of a pH adjuster, a surfactant, and a bactericide.

[0063] The through-silicon via (TSV) copper film chemical mechanical polishing slurry described in this application further includes a pH adjuster. In some specific implementations, the pH adjuster is an acid adjuster, selected from organic or inorganic acids. The inorganic acid is selected from one or more of hydrochloric acid, phosphoric acid, nitric acid, or sulfuric acid, and the organic acid is selected from one or more of succinic acid, malonic acid, tartaric acid, or gluconic acid. In some specific implementations, the pH adjuster is a base adjuster, selected from inorganic or organic bases. The inorganic base is selected from one or more of ammonium hydroxide, potassium hydroxide, or sodium hydroxide, and the organic base is selected from one or more of tetraalkylammonium hydroxide, ethanolamine, ethylenediamine, or diethylamine. The pH adjuster is used to adjust the TSV copper film chemical mechanical polishing slurry, resulting in a pH value of 5 to 9, specifically 5, 6, 7, 7.3, 8, or 9. In some specific implementations, the pH of the TSV copper film chemical mechanical polishing slurry is 6 to 8.

[0064] The chemical mechanical polishing slurry for through-silicon via (TSV) copper films described in this application also includes a bactericide. In some specific implementations, the bactericide includes, but is not limited to, 5-chloro-2-methyl-4-isothiazolin-3-one and / or 2-methyl-4-isothiazolin-3-one. This application does not have any special requirements for the selection of the bactericide.

[0065] The chemical mechanical polishing slurry for through-silicon via (TSV) copper films described in this application also includes a surfactant. In some specific implementations, the surfactant is selected from one or more of alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfates, alkyl phosphates, sodium fatty alcohol polyoxyethylene ether sulfate, sarcosinates, taurines, polyacrylic acid, polyethers, polyoxyethylene ether phosphates, polyethylene glycol, polyvinyl alcohol, polyvinyl butyral, cellulose, polyethyleneimine, polyvinylpyrrolidone, ethoxypropoxylated fatty alcohols, alkoxylated branched fatty alcohols, linear secondary alcohol polyoxyethylene ethers, polyethylene glycol stearate, acetylacetonate ethoxylated compounds, alkyl ammonium salts, or alkylpyridinium salts. This application does not have special requirements for the selection of surfactants.

[0066] This application also provides the application of the above-mentioned through-silicon via copper film chemical mechanical polishing slurry for semiconductor substrates with copper plating, copper wiring or through-silicon via copper surfaces, including: contacting the through-silicon via copper film chemical mechanical polishing slurry with the semiconductor substrate to be polished and performing chemical mechanical polishing treatment; the surface of the semiconductor substrate to be polished includes at least one copper or at least a portion of a copper-containing surface.

[0067] In some specific implementations, the semiconductor substrate to be polished further includes a barrier layer and / or a dielectric layer, wherein the barrier layer comprises one or more of Ta, TaN, Ti, TiN, or SiN; and the dielectric layer comprises one or more of TEOS, low-k, or ultra-low-k dielectrics.

[0068] The present application is further illustrated below with reference to embodiments. The scope of protection of the present application is not limited to the following embodiments.

[0069] The specific components of the through-silicon via (TSV) copper film chemical mechanical polishing (CMP) slurry in the embodiments and comparative examples of this application are calculated based on the content of pure substances and prepared according to the formulas given in Tables 1-2, with the remainder being water (the percentages in the tables all represent mass percentages). All components are mixed evenly, and the pH is adjusted to the required value using nitric acid or potassium hydroxide before further mixing to obtain the TSV copper film CMP slurry. The content of each component in the TSV copper film CMP slurry represents the actual concentration used during the polishing process; commercially available products can be appropriately concentrated.

[0070] Table 1

[0071]

[0072] Table 2

[0073]

[0074] The performance of the through-silicon via (TSV) copper film chemical mechanical polishing slurries provided in Examples 1-7 and the through-silicon via (TSV) copper film polishing slurries provided in Comparative Examples 1-6 was tested using the following methods:

[0075] The samples to be polished included 8-inch copper (Cu) wafer blanks, 8-inch copper 854 structure wafers, 8-inch tantalum (Ta) wafer blanks, 8-inch tantalum nitride (TaN) wafer blanks, 8-inch titanium (Ti) wafer blanks, 8-inch titanium nitride (TiN) wafer blanks, and 8-inch silicon oxide (TEOS) wafer blanks. The polishing pressure was 2 psi. The polishing time for blank wafers was uniformly 1 minute, and the 854 structure wafers were polished until no copper film residue remained. The polishing machine used was a SIZONE TENMS-200 Plus, the polishing pad was an IC1010, the polishing head and polishing disk speeds were 93 rpm and 87 rpm respectively, and the polishing fluid flow rate was 150 ml / min.

[0076] The metal film thickness measurement instrument was a NAPSON RG3000, which used 49 points to measure the change in film thickness before and after polishing, thereby calculating the polishing rate. The dielectric film thickness measurement instrument was a FILMETRICS F54-XYT-300, which also used 49 points to measure the change in film thickness before and after polishing, thereby calculating the polishing rate.

[0077] The butterfly-shaped indentation measuring machine is a KLA-Tencor P-17, which measures two feature patterns: 50um×50um and 10um×10um. The height difference between the two platforms relative to the middle indentation is the indentation value.

[0078] Comparative Examples 1-6 and Examples 1-7 were selected to polish Cu substrates and Cu structural sheets under the same conditions. At the same time, static corrosion tests were performed on the Cu substrates. The results of removal rate, corrosion rate and butterfly indentation value are listed in Table 3.

[0079] Table 3

[0080]

[0081] As shown in Table 3, for Comparative Examples 1-3, in the Cu polishing composition using glycine as a chelating agent and lauramidopropyl dimethylamine as a corrosion inhibitor, both the copper film removal rate and the butterfly indentation value increased with the increase of abrasive particle size. When the silica particle size increased from 41 nm to 103 nm, the copper film removal rate increased by 10.5% under a pressure of 2 psi. Simultaneously, the copper indentation values ​​on 50 μm × 50 μm and 10 μm × 10 μm patterns increased by 30.3% and 18.9%, respectively. In Comparative Examples 4-5 and Example 1, copper films were polished by mixing silica sols of 41 nm and 103 nm sizes in a specific ratio, while maintaining a constant proportion of abrasive in the polishing solution. The results show that when the large-particle abrasive accounts for 24% of the total abrasive (the mass ratio of large-particle abrasive to small-particle abrasive is 6:19) (Example 1), the copper film removal rate reaches its maximum value, with increases of 18.1% and 6.9% respectively compared to when small-particle and large-particle abrasives are present alone (Comparative Examples 1 and 3). Meanwhile, no significant change was observed in the copper indentation values ​​on the 50µm×50µm and 10µm×10µm patterns. These results indicate that the two particle sizes of abrasives have a synergistic effect on improving the copper removal rate. It is speculated that mixing silica sols of two particle sizes in a specific ratio increases the contact area between the abrasive and the copper film layer during polishing, thereby improving the copper removal rate. However, due to the low proportion of large-particle abrasives, the butterfly-shaped indentation values ​​at the characteristic patterns did not change significantly. Compared to Example 1, in Comparative Example 4, large-particle abrasive accounted for 10% of the total abrasive (the mass ratio of large-particle abrasive to small-particle abrasive was 1:9), and the improvement in copper mold removal rate was limited. However, when the proportion of large-particle abrasive was further increased to 40% (Comparative Example 5, the mass ratio of large-particle abrasive to small-particle abrasive was 2:3), the butterfly-shaped indentation value at the feature pattern increased significantly. In Example 2, 41nm and 80nm silica sols were mixed in a specific ratio (the mass ratio of large-particle abrasive to small-particle abrasive was 6:19) and then polished on copper films. The results were similar; the copper film removal rate increased by 15.8% and 6.8% respectively compared to when small-particle and large-particle abrasives were present alone (Comparative Example 1 and Comparative Example 3), while no significant change was observed in the copper indentation value on 50um×50um and 10um×10um patterns. The above results indicate that only when the two abrasive particles of different sizes are in a specific mass ratio of (1:4) to (3:7) can a high copper removal rate be maintained while a low butterfly indentation value be achieved.

[0082] The results of Comparative Example 6 and Examples 1, 3-4 show that, using glycine as a chelating agent and a polishing composition in which silica sols of 41 nm and 103 nm sizes are mixed in a specific ratio, the use of the compound with the structure of Formula 1 provided by this invention as a corrosion inhibitor (Examples 1, 3-4) can maintain a high copper film removal rate, and the copper surface corrosion and post-polishing depression values ​​can be effectively controlled. However, when a nitrazole compound is used as a corrosion inhibitor (Comparative Example 6), although the copper depression value at the feature pattern is slightly improved, the copper mold removal rate decreases significantly, and the copper surface corrosion rate increases at room temperature. This indicates that, compared to traditional nitrazole corrosion inhibitors, the corrosion inhibitor provided by this invention can achieve a high and adjustable copper film removal rate under lower pressure conditions, significantly improving production efficiency, while effectively controlling copper surface corrosion and post-polishing depression values.

[0083] This is because traditional azole corrosion inhibitors tend to bind with copper films to form dense molecular films, significantly affecting the removal rate of the copper film layer and hindering subsequent cleaning processes. The novel corrosion inhibitor of this invention can effectively reduce both localized and overall copper corrosion, maintaining the original metallic luster of the copper surface. Furthermore, during polishing, under shear force, it continuously detaches from and re-bonds onto the copper surface in a "dynamic" manner, thus maintaining a high copper removal rate.

[0084] The results of Examples 5-7 show that adding the compounds with structures of Formula 2 and Formula 3 provided by this invention as butterfly depression inhibitors to the polishing composition slightly reduces the copper film removal rate, but still maintains a high removal rate under relatively low pressure. Simultaneously, surface corrosion and post-polishing depression values ​​are further improved. Therefore, in Cu polishing solutions using compounds of Formula 1 as corrosion inhibitors and amino acids and their derivatives as chelating agents, butterfly depression inhibitors of Formula 2 and Formula 3 can significantly enhance the inhibition of copper butterfly depressions. Furthermore, the butterfly depression inhibitors only slightly reduce the copper removal rate, but still maintain a high removal rate under low pressure. They also synergistically work with compounds of Formula 3 to provide anti-corrosion protection, thereby further improving copper surface corrosion.

[0085] The chemical mechanical polishing slurry for through-silicon via (TSV) copper films provided in Example 5 was used to measure the selectivity of the Cu film relative to other barrier layers such as Ta, TaN, Ti, and TiN, as well as dielectric films such as TEOS. Table 4 lists the selectivity results when using a pressure of 2 psi.

[0086] Table 4

[0087]

[0088] As shown in Table 4, during chemical mechanical polishing, the polishing composition removed Cu films at a much higher rate than other substrate materials. This high selectivity in polishing is highly desirable for many applications requiring high copper film removal rates, such as TSV applications.

[0089] Based on the above test results, the through-silicon via copper film chemical mechanical polishing slurry in this application can remove the copper film layer at a relatively fast speed, and can effectively improve the local and overall corrosion of metal materials, and reduce the butterfly-shaped depressions of copper after polishing. It is worth mentioning that the concentrations of each component in the above embodiments are the actual amounts used in the polishing process. This system can be appropriately concentrated and kept in a stable state, so as to facilitate production, transportation and use at the client end.

[0090] The above description is merely a preferred embodiment of this application, but the scope of protection of this application is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in this application, based on the technical solution and application concept of this application, should be included within the scope of protection of this application.

Claims

1. A chemical mechanical polishing slurry for through-silicon via copper films, characterized in that, include: Abrasives, oxidants, chelating agents, corrosion inhibitors, and water; The abrasive in the through-silicon via (TSV) copper film chemical mechanical polishing slurry has a mass percentage of 0.002-20%, and is composed of large-diameter and small-diameter abrasive particles; the large-diameter abrasive particle has a D... 50 The value is 70nm to 110nm, and the D of the small-particle abrasive is... 50 The value is 30nm to 50nm, and the mass ratio of the large-particle abrasive to the small-particle abrasive is (1:4) to (3:7). The pH of the chemical mechanical polishing solution for the through-silicon via copper film is 5-9; The corrosion inhibitor has the structure of Formula 1; ； Wherein, R1 is a straight-chain alkyl group from C7 to C17, R2 and R3 are each independently -H, -CH3, -CH2CH3 or -CH2CH2OH, and m is 2 or 3; The abrasive includes SiO2; The oxidant includes one or more of hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, and sodium perchlorate. The chelating agent includes one or more of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, or iminodiacetic acid. The oxidant contains 0.1% to 10% by mass in the chemical mechanical polishing slurry for through-silicon via copper films. The chelating agent has a mass percentage of 0.1% to 15% in the chemical mechanical polishing slurry for through-silicon via copper films; The corrosion inhibitor has a mass percentage content of 0.005~1% in the chemical mechanical polishing slurry for through-silicon via copper films.

2. The chemical mechanical polishing slurry for through-silicon via copper films according to claim 1, characterized in that, The corrosion inhibitors include one or more of N-(3-aminopropyl)dodecanoamide, N-(3-aminopropyl)octanoamide, octanoamide-propyl dimethyl tertiary amine, decanoamide-propyl dimethyl tertiary amine, N-[2-(2-hydroxyethylamino)ethyl]dodecanoamide, palmitamide-propyl diethylamine, myristamide-propyl dimethylamine, N-[2-(diethylamino)ethyl]stearamide, stearamide-propyl dimethylamine, stearamide-ethyl diethylamine, N-octadecanoyl ethylenediamine, or lauramide-propyl dimethylamine.

3. The chemical mechanical polishing slurry for through-silicon via copper films according to claim 1, characterized in that, The large-particle-size abrasive's D 50 The value is 80nm to 110nm, and the D of the small-particle abrasive is... 50 The value is 30nm to 50nm.

4. The chemical mechanical polishing slurry for through-silicon via copper films according to claim 1, characterized in that, The pH of the chemical mechanical polishing solution for through-silicon via copper films is 6-8.

5. The chemical mechanical polishing slurry for through-silicon via copper films according to claim 1, characterized in that, The through-silicon via copper film chemical mechanical polishing slurry also includes a butterfly depression inhibitor, which is selected from compounds with structures of formula 2 and / or formula 3; ； R4 and R5 are each independently a C6 to C12 straight-chain or branched alkyl group, and M is Na, K or NH4.

6. The chemical mechanical polishing slurry for through-silicon via copper films according to claim 5, characterized in that, The butterfly-shaped depression inhibitor of Formula 2 includes potassium 7-tetradecyl sulfate, potassium 8-pentadecanyl sulfate, potassium 7-pentadecanyl sulfate, potassium 8-hexadecyl sulfate, potassium 7-hexadecyl sulfate, potassium 9-heptadecyl sulfate, potassium 8-heptadecyl sulfate, potassium 7-heptadecyl sulfate, potassium 9-octadecyl sulfate, potassium 8-octadecyl sulfate, potassium 7-octadecyl sulfate, potassium 10-nonadecanyl sulfate, potassium 9-nonadecanyl sulfate, potassium 8-nonadecanyl sulfate, potassium 7-nonadecanyl sulfate, potassium 10-eicosyl sulfate, potassium 9-eicosyl sulfate, potassium 8-eicosyl sulfate, potassium 11-tetradecyl sulfate, potassium 10- Potassium hexadecyl sulfate, 9-monodecyl sulfate, 11-monodecyl sulfate, 10-monodecyl sulfate, 12-tridecyl sulfate, 11-tridecyl sulfate, 12-tetradecyl sulfate, 7-tetradecyl ammonium sulfate, 8-pentadecanyl ammonium sulfate, 7-pentadecanyl ammonium sulfate, 8-hexadecyl ammonium sulfate, 7-hexadecyl ammonium sulfate, 9-heptadecyl ammonium sulfate, 8-heptadecyl ammonium sulfate, 7-heptadecyl ammonium sulfate, 9-octadecyl ammonium sulfate, 8-octadecyl ammonium sulfate, 7-octadecyl ammonium sulfate, 10-nonadecanyl ammonium sulfate, 9-nonadecanyl ammonium sulfate, 8-decyl... Nonylammonium sulfate, 7-nonadecanylammonium sulfate, 10-eicosylammonium sulfate, 9-eicosylammonium sulfate, 8-eicosylammonium sulfate, 11-tetranylammonium sulfate, 10-tetranylammonium sulfate, 9-tetranylammonium sulfate, 11-tetranylammonium sulfate, 10-tetranylammonium sulfate, 12-tetranylammonium sulfate, 11-tetranylammonium sulfate, 12-tetranylammonium sulfate, 11-tetranylammonium sulfate, 12-tetranylammonium sulfate, 7-tetraalkylammonium sulfate, 8-pentadecanylammonium sulfate, 7-pentadecanylammonium sulfate, 8-hexadecylammonium sulfate, 7-hexadecylammonium sulfate, 9-heptadecylammonium sulfate, 8-heptadecylammonium sulfate Sodium 7-heptadecyl sulfate, sodium 9-octadecyl sulfate, sodium 8-octadecyl sulfate, sodium 7-octadecyl sulfate, sodium 10-nonadecanyl sulfate, sodium 9-nonadecanyl sulfate, sodium 8-nonadecanyl sulfate, sodium 7-nonadecanyl sulfate, sodium 10-eicosyl sulfate, sodium 9-eicosyl sulfate, sodium 8-eicosyl sulfate, sodium 11-tetradecyl sulfate, sodium 10-tetradecyl sulfate, sodium 9-tetradecyl sulfate, sodium 11-didecyl sulfate, sodium 10-didecyl sulfate, sodium 12-tridecyl sulfate, sodium 11-tridecyl sulfate, or sodium 12-tetradecyl sulfate; The butterfly-shaped depression inhibitors of Formula 3 include potassium 2-hexyl-1-nonyl sulfate, potassium 2-heptyl-1-nonyl sulfate, potassium 2-hexyl-1-decyl sulfate, potassium 2-heptyl-1-decyl sulfate, potassium 2-octyl-1-decyl sulfate, potassium 2-hexyl-1-undecyl sulfate, potassium 2-heptyl-1-undecyl sulfate, potassium 2-octyl-1-undecyl sulfate, potassium 2-hexyl-1-dodecyl sulfate, potassium 2-heptyl-1-dodecyl sulfate, ammonium 2-hexyl-1-nonyl sulfate, ammonium 2-heptyl-1-nonyl sulfate, ammonium 2-hexyl-1-decyl sulfate, ammonium 2-heptyl-1-decyl sulfate, ammonium 2-octyl-1-decyl sulfate. The sodium sulfate is one or more of the following: 2-hexyl-1-undecyl sulfate, 2-heptyl-1-undecyl sulfate, 2-octyl-1-undecyl sulfate, 2-hexyl-1-dodecyl sulfate, 2-heptyl-1-dodecyl sulfate, 2-hexyl-1-nonyl sulfate, 2-heptyl-1-nonyl sulfate, 2-hexyl-1-decyl sulfate, 2-heptyl-1-decyl sulfate, 2-octyl-1-decyl sulfate, 2-hexyl-1-undecyl sulfate, 2-heptyl-1-undecyl sulfate, 2-octyl-1-undecyl sulfate, 2-hexyl-1-dodecyl sulfate, or 2-heptyl-1-dodecyl sulfate.

7. The chemical mechanical polishing slurry for through-silicon via copper films according to claim 5, characterized in that, The mass percentage of the butterfly-shaped indentation inhibitor in the polishing slurry is 0.001~1%.

8. The chemical mechanical polishing slurry for through-silicon via copper films according to claim 1, characterized in that, The through-silicon via copper film chemical mechanical polishing slurry also includes one or more of the following: pH adjuster, surfactant, and bactericide.

9. The application of a chemical mechanical polishing slurry for through-silicon via copper films as described in any one of claims 1 to 8, characterized in that, Semiconductor substrates for copper plating, copper wiring, or through-silicon via (TSV) copper surfaces include: contacting a TSV copper film chemical mechanical polishing slurry with the semiconductor substrate to be polished and performing a chemical mechanical polishing treatment; the surface of the semiconductor substrate to be polished includes at least one copper or at least a portion of a copper-containing surface.

10. The application according to claim 9, characterized in that, The semiconductor substrate to be polished further includes a barrier layer and / or a dielectric layer, wherein the barrier layer comprises one or more of Ta, TaN, Ti, TiN or SiN; and the dielectric layer comprises one or more of TEOS, low k or ultra-low k.

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