Low recessed through-silicon via copper film chemical mechanical polishing liquid and application thereof

Abstract

The application discloses a low-recess silicon through-hole copper film chemical mechanical polishing liquid and application thereof. The low-recess silicon through-hole copper film chemical mechanical polishing liquid comprises abrasive particles, an oxidizing agent, a chelating agent, a corrosion inhibitor, a butterfly-shaped recess inhibitor and water; the butterfly-shaped recess inhibitor is selected from structural compounds of formula 1 and / or formula 2, two C6-C12 hydrophobic alkyl chains of the structural compounds isolate the attack of chemical substances on the copper film layer, have more excellent steric hindrance than linear alkyl sulfate with the same number of carbon atoms, can synergistically act with the corrosion inhibitor to further reduce the copper corrosion rate, and thus improve product yield. Meanwhile, the butterfly-shaped recess inhibitor is adsorbed on the surface of the copper film layer in the groove, protects the copper film layer from being excessively removed in the over-polishing time, and thus significantly improves the butterfly-shaped recess after polishing. Although the overall removal rate of the copper film slightly decreases, high and adjustable copper removal rates can be achieved under lower down pressure, and production efficiency is ensured.

Description

Technical Field

[0001] This application relates to the field of polishing technology in semiconductor manufacturing, and more particularly to a low-recession through-silicon via copper film chemical mechanical polishing slurry 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 improve production efficiency, avoiding localized and overall corrosion, and maintaining a relatively low butterfly depression value to provide a suitable process for subsequent barrier layer polishing.

[0004] However, as 3D packaging technology matures and through-silicon via (TSV) technology gains wider application, downstream manufacturers are placing higher demands on polishing processes. For example, the requirement for controlling the butterfly indentation value after polishing has increased from less than 2μm initially to less than 1μm or even lower now. However, in high-speed copper polishing applications, existing copper polishing slurries, while increasing the copper film removal rate, have failed to address issues such as localized or overall excessive corrosion of the copper and low butterfly indentation.

[0005] Therefore, developing a chemical mechanical polishing slurry that can improve the copper film removal rate while reducing the pitting problem 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 low-recession through-silicon via copper film chemical mechanical polishing slurry, 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 low-recession through-silicon via copper films, comprising: abrasive particles, oxidant, chelating agent, corrosion inhibitor, butterfly recess inhibitor, and water;

[0008] The butterfly-shaped indentation inhibitor is selected from compounds with structures of Formula 1 and / or Formula 2;

[0009] ;

[0010] Wherein, R1 and R2 are each independently C6 to C12 straight-chain or branched alkyl groups, and M is Na, K or NH4.

[0011] In some specific implementations, the butterfly depression inhibitor of Formula 1 includes potassium 7-tetradecyl sulfate, potassium 8-pentadedecyl sulfate, potassium 7-pentadedecyl 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-nonadedecyl sulfate, potassium 9-nonadedecyl sulfate, potassium 8-nonadedecyl sulfate, potassium 7-nonadedecyl 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 ...1-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 19-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;

[0012] The butterfly-shaped depression inhibitors of Formula 2 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.

[0013] In some specific implementations, the corrosion inhibitor includes compounds with a formula of 3 and / or heteroaromatic compounds containing nitrogen atoms;

[0014] ;

[0015] Wherein, R3 is a straight-chain alkyl group from C7 to C17, R4 and R5 are each independently -H, -CH3, -CH2CH3 or -CH2CH2OH, and m is 2 or 3.

[0016] In some specific implementations, the corrosion inhibitor of Formula 3 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, myristamide propyl dimethylamine, N-[2-(diethylamino)ethyl]stearamide, stearamide propyl dimethylamine, stearamide ethyl diethylamine, N-octadecanoyl ethylenediamine, or lauramide propyl dimethylamine;

[0017] The nitrogen-containing heteroaromatic compounds include one or more of 1,2,4-triazole, aminotriazole, 3,5-diamino-1,2,4-triazole, benzotriazole, 5-carboxybenzotriazole, 1-hydroxy-benzotriazole, tetrazolium, 5-aminotetrazolium, 2-methyl-5-aminotetrazolium, 1-aminotetrazolium, imidazole, benzimidazole, 2-aminoimidazole, pyrazole, 2-carboxypyrazole, or 3-aminopyrazole.

[0018] In some specific implementations, the abrasive particles include one or more of SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3 and their co-formed products, soft abrasive particles based on organic polymers, and particles with surface modification by silane coupling agents.

[0019] And / or, the particle size of the abrasive particles is 20~200nm;

[0020] 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;

[0021] And / or, the chelating agent includes one or more amino acids and amino acid derivatives;

[0022] And / or, the pH of the chemical mechanical polishing solution for the low-recessed silicon through-hole copper film is 5-9.

[0023] In some specific implementations, the abrasive particles include one or more of SiO2, Al2O3, and CeO2;

[0024] And / or, the particle size of the grinding particles is 30~150nm;

[0025] And / or, the oxidant includes one or more of hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, or sodium perchlorate;

[0026] 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;

[0027] And / or, the pH of the chemical mechanical polishing solution for the low-recessed silicon through-hole copper film is 6-8.

[0028] In some specific implementations, the abrasive particles in the chemical mechanical polishing slurry for low-recessed silicon via copper films are 0.002% to 20% by mass.

[0029] And / or, the oxidant has a mass percentage of 0.1-10% in the chemical mechanical polishing slurry for low-recessed silicon via copper films;

[0030] And / or, the chelating agent has a mass percentage content of 0.1% to 15% in the chemical mechanical polishing slurry for low-recessed silicon through-hole copper films;

[0031] And / or, the corrosion inhibitor has a mass percentage content of 0.005~1% in the chemical mechanical polishing slurry for low-recessed silicon via copper films;

[0032] And / or, the butterfly-shaped depression inhibitor has a mass percentage content of 0.001~1% in the chemical mechanical polishing slurry for low-depression silicon through-hole copper films.

[0033] In some specific implementations, the low-recessed silicon through-hole copper film chemical mechanical polishing slurry also includes one or more of the following: pH adjuster, surfactant, and bactericide.

[0034] This application also provides an application of the low-recession through-silicon via copper film chemical mechanical polishing slurry as described above, for use on the surface of a semiconductor substrate with copper plating, copper wiring, or through-silicon via copper, comprising the following steps: contacting the low-recession 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 contains at least one copper or at least a portion of a copper-containing surface.

[0035] 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.

[0036] The low-recession chemical mechanical polishing slurry for TSV (Through Silicon Via) copper film polishing provided in this application uses compounds with structures of Formula 1 and Formula 2 as butterfly-shaped depression inhibitors. These compounds have two C6-C12 alkyl chains, and their hydrophobic portions can isolate the copper film layer from chemical attack, exhibiting superior steric barrier properties compared to straight-chain alkyl sulfates with the same number of carbon atoms. On one hand, by adsorbing onto the surface of the copper film layer within the trench, it protects it from excessive removal during the over-polishing time, thus significantly improving the butterfly-shaped depressions after polishing (copper depression values ​​as low as 509 Å on 50 μm × 50 μm patterns and as low as 367 Å on 10 μm × 10 μm patterns). Because it also adsorbs onto the copper layer surface at higher steps, the overall copper removal rate decreases slightly, but a high and adjustable copper metal removal rate can still be achieved at relatively low pressures (copper removal rate adjustable from 15424 to 35359 Å / min at 2 psi pressure), thereby improving production efficiency. On the other hand, the butterfly-shaped depression inhibitors of Formula 1 and Formula 2 can synergistically exert anti-corrosion effects with compounds of Formula 3 and nitrogen-containing heteroaromatic compounds. Based on the reduction of local and overall corrosion of the metal material by the corrosion inhibitor, the surface loss of the Cu film is further improved (the copper corrosion rate can be as low as 7 Å / min), thereby improving product yield. Furthermore, the chemical mechanical polishing slurry for low-depression silicon through-hole copper films is generally weakly alkaline to neutral, which can effectively reduce the corrosion of the polishing slurry on the machine. It also possesses excellent polishing selectivity, enabling highly selective removal of the copper film relative to barrier layers (such as Ta, TaN, Ti, TiN, or SiN) and dielectric layers (such as TEOS, low-k, or ultra-low k). Detailed Implementation

[0037] 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.

[0038] 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.

[0039] 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 may be performed simultaneously.

[0040] 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.

[0041] 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.

[0042] This application provides a chemical mechanical polishing slurry for low-recession through-silicon via copper films, comprising: abrasive particles, oxidant, chelating agent, corrosion inhibitor, butterfly recess inhibitor, and water;

[0043] The butterfly-shaped indentation inhibitor is selected from compounds with structures of Formula 1 and / or Formula 2;

[0044] ;

[0045] Wherein, R1 and R2 are each independently C6 to C12 straight-chain or branched alkyl groups (which can be C6, C7, C8, C9, C10, C11, or C12), and M is Na, K, or NH4.

[0046] 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.

[0047] Preferably, the butterfly depression inhibitor of Formula 1 comprises sodium 7-tetradecyl sulfate, sodium 8-pentadedecyl sulfate, potassium 7-pentadedecyl 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-nonadedecyl sulfate, potassium 9-nonadedecyl sulfate, potassium 8-nonadedecyl sulfate, potassium 7-nonadedecyl 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.

[0048] Preferably, the butterfly depression inhibitor of Formula 2 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, or one or more of these.

[0049] 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.

[0050] In some specific implementations, the butterfly indentation inhibitor can be sodium 7-tetradecyl sulfate. Sodium 8-pentadecanyl sulfate Sodium 7-pentadecanyl sulfate Sodium 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.

[0051] 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%.

[0052] The chemical mechanical polishing slurry for low-recessed silicon through-hole copper films described in this application includes corrosion inhibitors. In some specific implementations, compounds with a formula 3 structure and / or heteroaromatic compounds containing nitrogen atoms are used.

[0053] ;

[0054] Wherein, R3 is a straight-chain alkyl group from C7 to C17 (which can be C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17), R4 and R5 are each independently -H, -CH3, -CH2CH3 or -CH2CH2OH, and m is 2 or 3.

[0055] Formula 3 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 3 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.

[0056] In some specific implementations, the corrosion inhibitor of Formula 3 can be one or more of the following: 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.

[0057] The nitrogen-containing heteroaromatic compounds include, but are not limited to, triazoles and their derivatives, benzotriazoles and their derivatives, tetrazolium and its derivatives, imidazoles and their derivatives, and pyrazoles and their derivatives. In some specific implementations, the nitrogen-containing heteroaromatic compounds may be one or more of the following: 1,2,4-triazole, aminotriazole, 3,5-diamino-1,2,4-triazole, benzotriazole, 5-carboxybenzotriazole, 1-hydroxy-benzotriazole, tetrazolium, 5-aminotetrazolium, 2-methyl-5-aminotetrazolium, 1-aminotetrazolium, imidazole, benzimidazole, 2-aminoimidazolium, pyrazole, 2-carboxypyrazole, or 3-aminopyrazole.

[0058] Preferably, the corrosion inhibitor has a mass percentage content of 0.005% to 1%, which 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%, and is more preferably 0.01% to 0.5%.

[0059] The chemical mechanical polishing slurry for low-recessed through-silicon via (TSV) copper films described in this application includes abrasive particles. In some specific implementations, the abrasive particles include, but are not limited to, one or more of the following: SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3 and 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 that can be used for chemical mechanical polishing. This application does not have special requirements for the selection of abrasive particles. The abrasive particles may have narrow or wide particle size distributions, and may have various sizes and different shapes. The shapes of the abrasive particles include spherical, cocoon-shaped, string-shaped, curved, and various other shapes. This application does not have special requirements for the shape of the abrasive particles. In some specific implementations, the particle size of the abrasive particles is from 20 nm to 200 nm, and can be 20 nm, 30 nm, 50 nm, 60 nm, 70 nm, 80 nm, 100 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, or 200 nm, preferably 30 to 150 nm. In some specific implementations, the abrasive particles include one or more of SiO2, Al2O3, and CeO2, and the particle size of the abrasive particles is 30 to 150 nm. The mass percentage of the grinding particles is from 0.002% to 20%, and 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%, 20%, preferably from 0.02% to 2%.

[0060] The chemical mechanical polishing slurry for low-recessed silicon through-hole copper films described in this application includes an oxidant. In some specific implementations, 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, hypobromite, bromic acid, bromate, perbromic acid, perbromite, hypoiodic acid, hypoiodate, iodic acid, iodate, periodic acid, periodate, chromic acid, chromate, iron salts, copper salts, ferricyanide, or molybdates. In some specific implementations, the oxidant includes one or more of the following: hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, and sodium perchlorate. The oxidant 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%.

[0061] The chemical mechanical polishing slurry for low-recessed silicon through-hole 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 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 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%.

[0062] In some specific implementations, the low-recessed silicon through-hole copper film chemical mechanical polishing slurry also includes one or more of the following: pH adjuster, surfactant, and bactericide.

[0063] The chemical mechanical polishing slurry for low-recessed silicon via copper films 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 an alkali adjuster, selected from inorganic or organic alkalis. The inorganic alkali is selected from one or more of ammonium hydroxide, potassium hydroxide, or sodium hydroxide, and the organic alkali is selected from one or more of tetraalkylammonium hydroxide, ethanolamine, ethylenediamine, or diethylamine. The pH adjuster is used to adjust the pH of the low-recessed silicon via 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 low-recessed silicon via copper film chemical mechanical polishing slurry is 6 to 8.

[0064] The chemical mechanical polishing slurry for low-recessed silicon through-hole 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 low-recessed silicon through-hole 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 aforementioned low-recession through-silicon via (TSV) copper film chemical mechanical polishing slurry for use on semiconductor substrates with copper plating, copper wiring, or TSV copper surfaces, comprising: contacting the low-recession TSV 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.

[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 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.

[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 low-recessed silicon through-hole copper film chemical mechanical polishing 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 1-4, with the balance 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 being mixed evenly to obtain the low-recessed silicon through-hole copper film chemical mechanical polishing slurry. The content of each component in the low-recessed silicon through-hole copper film chemical mechanical polishing 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] Table 3

[0075]

[0076] Table 4

[0077]

[0078] The performance of the low-recession through-silicon via (TSV) copper film chemical mechanical polishing slurries provided in Examples 1-11 and the TSV copper film polishing slurries provided in Comparative Examples 1-11 was tested using the following methods:

[0079] 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 the blank wafers was uniformly 1 min, 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.

[0080] 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.

[0081] 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.

[0082] The test results are shown in Table 5-8.

[0083] Test 1: Effect of butterfly-shaped indentation inhibitor on copper removal rate and corrosion rate;

[0084] Comparative Examples 1-9 and Examples 1-11 of this application were selected to perform polishing and static etching tests on Cu substrates under the same conditions. The results of removal rate and etching rate are listed in Table 5.

[0085] Table 5

[0086]

[0087] Table 5 shows that Comparative Example 1, lacking both corrosion inhibitors and butterfly indentation inhibitors, exhibited excessively high copper corrosion rates and severe surface corrosion. Compared to Comparative Example 1, the polishing solutions of Comparative Examples 2-7, containing compounds of Formula 3, nitrogen-containing heteroaromatic compounds, or combinations thereof, acted as corrosion inhibitors, resulting in a decrease in the copper film removal rate and an improvement in the copper corrosion rate. The only difference between Comparative Examples 4 and 8-9 was the type of chelating agent, indicating that the aforementioned effects are generally present when amino acids and their derivatives are used as chelating agents.

[0088] Comparative Example 2's through-silicon via (TSV) copper film polishing solution contained 1,2,4-triazole as a corrosion inhibitor. Example 5 differed from Comparative Example 2 in that it also contained sodium 9-heptadecyl sulfate as a butterfly-shaped depression inhibitor. Compared to Comparative Example 2, Example 5 showed a slight decrease in Cu film removal rate at 2 psi pressure, while the Cu film corrosion rate at room temperature decreased to 45 Å / min. Comparative Example 3's polishing solution contained benzotriazole as a corrosion inhibitor. Example 6 differed from Comparative Example 3 in that it also contained sodium 9-heptadecyl sulfate as a butterfly-shaped depression inhibitor. Compared to Comparative Example 3, Example 6 showed a slight increase in Cu film removal rate at 2 psi pressure, while the Cu film corrosion rate at room temperature decreased to 31 Å / min. Å / min; The polishing solution of Comparative Example 4 contains lauramidopropyl dimethylamine as a corrosion inhibitor. The difference between Examples 1-4 and Comparative Example 4 is that it also contains sodium 9-heptadecyl sulfate, sodium 7-tetradecyl sulfate, and sodium 2-hexyl-1-dodecyl sulfate as butterfly depression inhibitors. Compared with Comparative Example 4, the Cu film removal rate of Examples 1-4 decreased slightly under a pressure of 2 psi, while the Cu film corrosion rate at room temperature could be reduced to as low as 25 Å / min. Similarly, analysis of the data of Comparative Examples 5 and 7, Comparative Examples 6 and 8, and Comparative Examples 7 and 9 shows that in Cu polishing compositions with glycine as a chelating agent and compounds of Formula 3, nitrogen-containing heteroaromatic compounds, or combinations thereof as corrosion inhibitors, the addition of butterfly depression inhibitors of Formula 1 and Formula 2 slightly decreases the copper film removal rate, but still maintains a high removal rate under relatively low pressure (2 psi). At the same time, the surface corrosion phenomenon is further improved, indicating that the butterfly depression inhibitor can promote the anti-corrosion effect of the corrosion inhibitor, and the two have a synergistic effect.

[0089] The only difference between Comparative Examples 8-9 and Comparative Example 4 is the type of chelating agent. The only difference between Example 10 and Comparative Example 8, and between Example 11 and Comparative Example 9 is the addition of a butterfly depression inhibitor. As can be seen from the results of Comparative Examples 8-9 and Examples 10-11, the butterfly depression inhibitor provided in this application has a similar effect when other amino acids or their derivatives are used as chelating agents.

[0090] In summary, the butterfly-shaped indentation inhibitor only slightly reduces the copper removal rate, but still maintains a high removal rate under low pressure. It can also synergize with compounds of Formula 3 and nitrogen-containing heteroaromatic compounds to exert an anti-corrosion effect, thereby further improving the corrosion phenomenon on the copper surface. Moreover, this effect is common when amino acids and their derivatives are used as chelating agents.

[0091] Test 2: The effect of butterfly-shaped indentation inhibitor on copper indentation value;

[0092] Comparative Examples 4, 10-11 and Examples 1-4 were selected, and Cu structural sheets were polished under the same conditions. The results of the butterfly-shaped indentation values ​​are listed in Table 6.

[0093] Table 6

[0094]

[0095] As shown in Table 6, the results of Comparative Examples 4, 11, and 2 indicate that the addition of alkyl sulfates to the Cu polishing composition, which uses glycine as a chelating agent and lauramidopropyl dimethylamine as a corrosion inhibitor, can improve the butterfly-shaped indentation value of the polished Cu structure sheet. Compared to Comparative Example 4, in Comparative Example 11, the addition amount of sodium heptadecanyl sulfate (a straight-chain alkyl sulfate with seventeen carbon atoms) was 0.09%, resulting in a -33.0% decrease in copper indentation value on a 50µm × 50µm pattern and a -26.8% decrease on a 10µm × 10µm pattern. In Example 2, the addition amount of the branched alkyl sulfate 9-heptadecanyl sulfate (with the same number of carbon atoms) resulted in a -47.3% and -38.9% decrease in copper indentation value on a 50µm × 50µm pattern and a 10µm × 10µm pattern, respectively, indicating that branched alkyl sulfates (Formula 1) can significantly enhance the inhibition of copper butterfly-shaped indentations. In Example 4, sodium 2-hexyl-1-dodecyl sulfate, at the same addition amount, showed a decrease in copper depression values ​​of -41.1% and -32.1% on 50µm×50µm and 10µm×10µm patterns, respectively. This indicates that when the sulfate ester group is bridged to the branched alkyl group via a methylene group (Formula 2), it can significantly enhance the suppression of copper butterfly depressions compared to straight-chain alkyl sulfates. Analysis of the above results shows that, compared to straight-chain alkyl sulfates, branched alkyl sulfates (Formulas 1 and 2) with the same number of carbon atoms have a superior steric barrier effect. During the polishing process of the Cu film, they are adsorbed onto the depressions on the film surface, preventing excessive removal of the copper.

[0096] The results of Comparative Example 10 and Example 3 yielded similar conclusions, showing that the branched alkyl sulfate 7-tetradecyl sulfate better protected the depressions on the Cu film surface compared to sodium tetradecyl sulfate, which has the same number of carbon atoms.

[0097] Comparative Examples 2-3, 5-9, and 5-11 were selected, and Cu structural sheets were polished under the same conditions. The results of the butterfly-shaped indentation values ​​are listed in Table 7.

[0098] Table 7

[0099]

[0100] As shown in Table 7, the polishing solution of Comparative Example 2 contains 1,2,4-triazole as a corrosion inhibitor. Example 5 differs from Comparative Example 2 in that it also contains sodium 9-heptadecyl sulfate as a butterfly-shaped depression inhibitor. Compared to Comparative Example 2, Example 5 shows a -50.1% reduction in copper depression value on a 50µm × 50µm pattern and a -44.0% reduction on a 10µm × 10µm pattern. The polishing solution of Comparative Example 3 contains benzotriazole as a corrosion inhibitor. Example 6 differs from Comparative Example 3 in that it also contains sodium 9-heptadecyl sulfate as a butterfly-shaped depression inhibitor. Compared to Comparative Example 3, Example 6 shows a -32.2% reduction in copper depression value on a 50µm × 50µm pattern and a -28.5% reduction on a 10µm × 10µm pattern. Similarly, analysis of data from Comparative Examples 5 and 7, 6 and 8, and 7 and 9 shows that when glycine is used as a chelating agent and compounds of Formula 3, nitrogen-containing heteroaromatic compounds, or combinations thereof are used as corrosion inhibitors in Cu polishing compositions, the addition of butterfly-shaped depression inhibitors of Formula 1 and 2 significantly improves the butterfly-shaped depression value of the polished Cu structure sheet.

[0101] The only difference between Comparative Examples 8-9 and Comparative Example 4 is the type of chelating agent. The only difference between Example 10 and Comparative Example 8, and between Example 11 and Comparative Example 9 is the addition of a butterfly depression inhibitor. As can be seen from the results of Comparative Examples 8-9 and Examples 10-11, the butterfly depression inhibitor provided by the present invention has a similar effect when other amino acids or their derivatives are used as chelating agents.

[0102] In summary, in Cu polishing solutions containing compounds of Formula 3, nitrogen-containing heteroaromatic compounds, or combinations thereof as corrosion inhibitors, and amino acids and their derivatives as chelating agents, the butterfly-shaped depression inhibitors of Formula 1 and Formula 2 can significantly enhance the inhibition of copper butterfly-shaped depressions.

[0103] Test 3: Selectivity of polishing slurry containing butterfly indentation inhibitor;

[0104] Example 2 was selected, and 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, was measured. Table 8 lists the selectivity results when a downpressure of 2 psi is used.

[0105] Table 8

[0106]

[0107] As shown in Table 8, 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.

[0108] Based on the above test results, the low-recession through-silicon via copper film chemical mechanical polishing slurry of 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.

[0109] 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 low-recession through-silicon via copper films, characterized in that, include: Abrasive particles, oxidant, chelating agent, corrosion inhibitor, butterfly indentation inhibitor, and water; The butterfly-shaped indentation inhibitor is selected from compounds with structures of Formula 1 and / or Formula 2; ； Wherein, R1 and R2 are each independently a C6 to C12 straight-chain or branched alkyl group, and M is Na, K or NH4; The corrosion inhibitors include compounds of formula 3 and / or heteroaromatic compounds containing nitrogen atoms; ； Wherein, R3 is a straight-chain alkyl group from C7 to C17, R4 and R5 are each independently -H, -CH3, -CH2CH3 or -CH2CH2OH, and m is 2 or 3; The grinding particles include SiO2; The particle size of the grinding particles is 20~200nm; The pH of the chemical mechanical polishing solution for the low-recessed silicon through-hole copper film is 5-9; The oxidant includes one or more of hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, or 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 abrasive particles constitute 0.002-20% of the total mass of the chemical mechanical polishing slurry for low-recessed silicon through-hole copper films. The oxidant has a mass percentage of 0.1-10% in the chemical mechanical polishing slurry for copper films in low-recessed silicon vias; The chelating agent has a mass percentage of 0.1% to 15% in the chemical mechanical polishing slurry for copper films in low-recessed silicon vias; The corrosion inhibitor has a mass percentage of 0.005-1% in the chemical mechanical polishing slurry for copper films in low-recessed silicon vias; The butterfly-shaped depression inhibitor has a mass percentage content of 0.001~1% in the chemical mechanical polishing slurry for low-depression silicon through-hole copper films.

2. The low-recession silicon through-hole copper film chemical mechanical polishing slurry according to claim 1, characterized in that, The butterfly-shaped depression inhibitor of Formula 1 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 2 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.

3. The chemical mechanical polishing slurry for low-recession silicon through-hole copper films according to claim 1, characterized in that, The corrosion inhibitor of Formula 3 includes one or more of the following: 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; The nitrogen-containing heteroaromatic compounds include one or more of 1,2,4-triazole, aminotriazole, 3,5-diamino-1,2,4-triazole, benzotriazole, 5-carboxybenzotriazole, 1-hydroxy-benzotriazole, tetrazolium, 5-aminotetrazolium, 2-methyl-5-aminotetrazolium, 1-aminotetrazolium, imidazole, benzimidazole, 2-aminoimidazole, pyrazole, 2-carboxypyrazole, or 3-aminopyrazole.

4. The low-recession silicon through-hole copper film chemical mechanical polishing slurry according to claim 1, characterized in that, The particle size of the grinding particles is 30~150nm; And / or, the pH of the chemical mechanical polishing solution for the low-recessed silicon through-hole copper film is 6-8.

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

6. The application of a low-recession silicon through-hole copper film chemical mechanical polishing slurry as described in any one of claims 1 to 5, characterized in that, A semiconductor substrate for use on the surface of copper plating, copper wiring, or through-silicon via (TSV) copper includes the following steps: contacting a low-recession TSV 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.

7. The application according to claim 6, 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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