A low-dishing chemical mechanical polishing slurry for through-silicon via copper films and uses thereof

Abstract

This invention discloses a chemical mechanical polishing (CMP) slurry for low-recession silicon through-hole (STB) copper films and its applications. The CMP slurry comprises abrasive particles, an oxidant, a chelating agent, a corrosion inhibitor, a butterfly depression inhibitor, and water. The butterfly depression inhibitor is selected from compounds having the structure of Formula 1 and / or Formula 2. Its two C6-C12 hydrophobic alkyl chains 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. It can synergistically work with the corrosion inhibitor to further reduce the copper corrosion rate, thereby improving product yield. Simultaneously, the butterfly depression inhibitor, adsorbed on the surface of the copper film layer within the trenches, protects it from excessive removal during the over-polishing time, thus significantly improving the butterfly depressions after polishing. Although the overall copper film removal rate decreases slightly, a high and adjustable copper removal rate can still be achieved at a relatively low downpressure, ensuring production efficiency.

Description

Technical Field

[0001] This invention relates to the field of polishing technology in semiconductor manufacturing, and more particularly to a chemical mechanical polishing slurry for low-recession silicon through-hole copper films and its applications. Prior Technology

[0002] With the development of CMOS process technology, the feature size of components is gradually shrinking, and the circuit density is becoming 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] Creating through-silicon vias (TSVs) on the back of a wafer through a complex process is key to achieving three-dimensional stacking between wafers. The process mainly consists of the following steps: 1. Highly efficient etching creates numerous through-holes; 2. The borehole filling includes a dielectric layer, an adhesive layer, a barrier layer, and a metal layer; 3. Chemical Mechanical Polishing (CMP) is used to remove the overlying metal layer, achieving planarization and circuit continuity. Due to the significant depth of silicon vias (SIVs), the copper plating thickness in SIV processes is much greater than that of copper interconnects in integrated circuits, reaching 2-10 μm, or even tens of micrometers. Therefore, higher requirements are placed on the polishing process of the copper film layer: it must achieve a high copper removal rate to improve production efficiency, avoid localized and overall corrosion, and maintain a relatively low butterfly-shaped 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, fail 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 reduce the sinking problem while improving the copper film removal rate is a problem that those skilled in the art urgently need to solve. Summary of the Invention

[0006] In view of this, the present invention provides a low-recession silicon through-hole 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 invention provides a chemical mechanical polishing slurry for low-recession silicon through-hole copper films, comprising: abrasive particles, an oxidant, a chelating agent, a corrosion inhibitor, a butterfly depression inhibitor, and water; The butterfly-shaped indentation inhibitor is selected from compounds having the structure of Formula 1 and / or Formula 2; ; In this context, R1 and R2 are each independently a C6 to C12 straight-chain or branched alkyl group, and M is Na, K, or NH4.

[0008] In some specific embodiments, the butterfly depression inhibitor having the structure 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-eicosyl sulfate, potassium 12-eicosyl sulfate, potassium 13-eicosyl sulfate, potassium 14-eicosyl sulfate, potassium 15-eicosyl sulfate, potassium 16-eicosyl sulfate, potassium 17-eicosyl sulfate, potassium 18-eicosyl sulfate, potassium 19-eicosyl sulfate, potassium 10-eicosyl sulfate, potassium 19-eicosyl sulfate, potassium 10-eicosyl sulfate, potassium 19-eicosyl sulfate, potassium 10-eicosyl sulfate, potassium 19-eicosyl sulfate, potassium 11-eicosyl sulfate, potassium 12-eicosyl sulfate, potassium 11-eicosyl sulfate, potassium 12-eicosyl sulfate, potassium 13-eicosyl sulfate, potassium 14-eicosyl sulfate, potassium 15-eicosyl sulfate, potassium 16-eicosyl sulfate, potassium 17-eicosyl sulfate, potassium 18-eicosyl sulfate, potassium 19-eicosyl sulfate, potassium 11-eicosyl sulfate, potassium 19-eicosyl sulfate, Potassium monoalkyl 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-tetraalkyl sulfate, ammonium 8-pentadecanoalkyl sulfate, ammonium 7-pentadecanoalkyl 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-nonadecanoalkyl sulfate, ammonium 9-nonadecanoalkyl 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-heptadecylammonium sulfate Sodium, 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-trialkyl sulfate, sodium 11-tetradecyl sulfate, and sodium 12-tetradecyl sulfate;

[0009] The butterfly-shaped depression inhibitor having the structure of Formula 2 includes: 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 following are one or more of the following: 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, and 2-heptyl-1-dodecyl sulfate.

[0010] In some specific embodiments, the corrosion inhibitor includes compounds having the structure of Formula 3 and / or heteroaromatic compounds containing nitrogen atoms; Equation 3; 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.

[0011] In some specific embodiments, the corrosion inhibitor having the structure of Formula 3 includes one or more of the following: N-(3-aminopropyl)dodecanoylamine, N-(3-aminopropyl)octylamine, octylaminopropyl dimethyl tertiary amine, decaaminopropyl dimethyl tertiary amine, N-[2-(2-hydroxyethylamino)ethyl]dodecanoylamine, palmitamide propyl diethylamine, myristamide propyl dimethylamine, N-[2-(diethylamino)ethyl]stearylamine, stearamide propyl dimethylamine, stearamide ethyl diethylamine, N-octadecylamide ethylenediamine, and laurylamide propyl dimethylamine;

[0012] The nitrogen-containing heteroaromatic compounds include 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-aminotetrazole, 2-methyl-5-aminotetrazole, 1-aminotetrazole, imidazole, benzimidazole, 2-aminoimidazolium, pyrazole, 2-carboxypyrazole, and 3-aminopyrazole.

[0013] In some specific embodiments, the abrasive particles include one or more of SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3 or products formed therefrom, soft abrasive particles based on organic polymers, and particles surface-modified with silane coupling agents; And / or, the particle size of the abrasive particles is 20~200nm; And / or, 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, hypobromicate, bromic acid, bromate, perbromic acid, perbromicate, hypoiodic acid, hypoiodide, iodic acid, iodate, periodic acid, periodate, chromic acid, chromate, iron salts, copper salts, ferricyanides, and molybdates; And / or, the chelating agent includes one or more of amino acids and amino acid derivatives; And / or, the pH of the chemical mechanical polishing solution for the low-recessed silicon through-hole copper film is 5-9.

[0014] In some specific embodiments, the abrasive particles include one or more of SiO2, Al2O3, and CeO2; And / or, the particle size of the abrasive particles is 30~150nm; And / or, the oxidant includes one or more of hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, and sodium perchlorate; 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, glutamic acid, aspartic acid, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, and iminodiacetic acid; And / or, the pH of the chemical mechanical polishing solution for the low-recessed silicon through-hole copper film is 6-8.

[0015] In some specific implementations, the content is expressed as a percentage by mass. The abrasive particles have a mass percentage of 0.002-20% in the chemical mechanical polishing slurry for low-recessed silicon through-hole copper films; And / or, the oxidant has a mass percentage of 0.1-10% in the chemical mechanical polishing slurry for low-recessed silicon through-hole copper films; And / or, the chelating agent has a mass percentage of 0.1-15% in the chemical mechanical polishing slurry for low-recessed silicon via copper films; And / or, the corrosion inhibitor has a mass percentage of 0.005~1% in the chemical mechanical polishing slurry for low-recessed silicon via copper films; And / or, the mass percentage of the butterfly-shaped depression inhibitor in the chemical mechanical polishing slurry for low-depression silicon through-hole copper films is 0.001~1%.

[0016] In some specific embodiments, the low-recessed silicon through-hole copper film chemical mechanical polishing slurry further includes one or more of a pH adjuster, a surfactant, and a bactericide.

[0017] The present invention also provides the use of the low-recessed silicon via copper film chemical mechanical polishing slurry as described above for semiconductor substrates on the surface of copper plating, copper wiring or silicon via copper, comprising the following steps: contacting the low-recessed 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 includes at least one copper surface or at least a portion of a copper-containing surface.

[0018] In some specific embodiments, 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 and SiN; and the dielectric layer includes one or more of TEOS, low-k materials and ultra-low-k materials.

[0019] The present invention provides a low-recession chemical mechanical polishing slurry for polishing TSV copper films, employing compounds of Formula 1 and / or Formula 2 as butterfly recess 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, it can protect the copper film layer adsorbed within the trenches from excessive removal during over-polishing, thereby significantly improving the butterfly recess after polishing (copper recess 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 film removal rate decreases slightly, but it can still achieve a high and adjustable copper metal removal rate under relatively low pressure (copper removal rate adjustable between 15424~35359 Å / min at 2 psi pressure), thereby improving production efficiency. On the other hand, the butterfly-shaped depression inhibitors of Formula 1 and / or Formula 2 can synergistically play an anti-corrosion role with compounds of Formula 3 and nitrogen-containing heteroaromatic compounds. On the basis of reducing local and overall corrosion of metal materials by corrosion inhibitors, the loss on the Cu film surface is further improved (copper corrosion rate can be as low as 7 Å / min), thereby improving product yield. In addition, the low-depression silicon through-hole copper film chemical mechanical polishing slurry is generally weakly alkaline to neutral, which can effectively reduce the corrosion of the polishing slurry on the machine. It also has excellent polishing selectivity, which can achieve high selective removal of 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). Implementation

[0020] 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 expressions "and / or" and "and / or" combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.

[0021] The terms “including,” “having,” or “containing,” including 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.

[0022] It should be understood that the order of the steps or the order in which certain actions are performed is not important as long as the invention remains operational. Furthermore, two or more steps or actions can be performed simultaneously.

[0023] Any and all instances or exemplary terms used herein, such as "for example" or "including," are intended only to better illustrate the invention and not to limit the scope of the invention. Nothing in this specification should be construed as indicating that any unclaimed element is essential to the practice of the invention.

[0024] Furthermore, the numerical ranges and parameters used to define the present invention are approximate values, and the relevant values ​​in the specific embodiments have been presented as precisely as possible. However, any value inevitably contains standard deviations due to individual test methods. Therefore, unless explicitly stated otherwise, 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.

[0025] This invention provides a chemical mechanical polishing slurry for low-recession silicon through-hole copper films, comprising: abrasive particles, an oxidant, a chelating agent, a corrosion inhibitor, a butterfly depression inhibitor, and water; The butterfly-shaped indentation inhibitor is selected from compounds having the structure of Formula 1 and / or Formula 2; ; R1 and R2 are each independently a C6 to C12 straight-chain or branched alkyl group (which can be C6, C7, C8, C9, C10, C11, or C12), and M is Na, K, or NH4.

[0026] 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 will decrease. Both of these will lead to "incompleteness" of the protective film layer.

[0027] Preferably, the butterfly depression inhibitor having the structure 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, 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 ammonium sulfate 8-Nondecylammonium sulfate, 7-Nondecylammonium sulfate, 10-Eicosylammonium sulfate, 9-Eicosylammonium sulfate, 8-Eicosylammonium sulfate, 11-Tyrodecylammonium sulfate, 10-Tyrodecylammonium sulfate, 9-Tyrodecylammonium sulfate, 11-Tyrodecylammonium sulfate, 10-Tyrodecylammonium sulfate, 12-Tyrodecylammonium sulfate, 11-Tyrodecylammonium sulfate, 12-Tyrodecylammonium sulfate, 11-Tyrodecylammonium sulfate, 12-Tyrodecylammonium sulfate, 7-Tetradecylammonium sulfate, 8-Pentadedecylammonium sulfate, 7-Pentadedecylammonium sulfate, 8-Hexadecylammonium sulfate, 7-Hexadecylammonium sulfate, 9-Heptadedecylammonium sulfate, 8-Heptadedecylammonium 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-tetranyl sulfate, sodium 10-tetranyl sulfate, sodium 9-tetranyl sulfate, sodium 11-tetranyl sulfate, sodium 10-tetranyl sulfate, sodium 12-tetranyl sulfate, sodium 11-tetranyl sulfate, and sodium 12-tetranyl sulfate.

[0028] Preferably, the butterfly depression inhibitor having the structure of Formula 2 comprises: 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 Ammonium, 2-hexyl-1-undecylammonium sulfate, 2-heptyl-1-undecylammonium sulfate, 2-octyl-1-undecylammonium sulfate, 2-hexyl-1-dodecylammonium sulfate, 2-heptyl-1-dodecylammonium sulfate, 2-hexyl-1-nonylsulfonate, 2-heptyl-1-nonylsulfonate, 2-hexyl-1-decylsulfonate, 2-heptyl-1-decylsulfonate, 2-octyl-1-decylsulfonate, 2-hexyl-1-undecylsulfonate, 2-heptyl-1-undecylsulfonate, 2-octyl-1-undecylsulfonate, 2-hexyl-1-dodecylsulfonate, and 2-heptyl-1-dodecylsulfonate, one or more of these.

[0029] The butterfly-shaped depression inhibitor provided by this invention 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, by adsorbing onto the surface of the copper film layer within the trench, protects it from excessive removal during the over-polishing time, 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 pressure, ensuring production efficiency.

[0030] In some specific embodiments, the butterfly indentation inhibitor can be sodium 7-tetradecyl sulfate CH3(CH2)5CH(OSO3Na)(CH2)6CH3, sodium 8-pentadecanyl sulfate CH3(CH2)6CH(OSO3Na)(CH2)6CH3, sodium 7-pentadecanyl sulfate CH3(CH2)5CH(OSO3Na)(CH2)7CH3, sodium 8-hexadecyl sulfate CH3(CH2)6CH(OSO3Na)(CH2)7CH3, sodium 7-hexadecyl sulfate CH3(CH2)5CH(OSO3Na)(CH2)8CH3, or sodium 9-heptadecyl sulfate CH3(CH2)7CH(OSO3Na)(CH2)7CH3 Sodium heptadecanyl sulfate CH3(CH2)6CH(OSO3Na)(CH2)8CH3, sodium heptadecanyl sulfate CH3(CH2)5CH(OSO3Na)(CH2)9CH3, sodium 9-octadecyl sulfate CH3(CH2)7CH(OSO3Na)(CH2)8CH3, sodium 8-octadecyl sulfate CH3(CH2)6CH(OSO3Na)(CH2)9CH3, sodium 7-octadecyl sulfate CH3(CH2)5CH(OSO3Na)(CH2)10CH3, sodium 10-nonadecanyl sulfate CH3(CH2)8CH(OSO3Na)(CH2)8CH3, sodium 9-nonadecanyl sulfate CH3(CH2)7C H(OSO3Na)(CH2)9CH3, 8-Nondecyl sulfate CH3(CH2)6CH(OSO3Na)(CH2)10CH3, 7-Nondecyl sulfate CH3(CH2)5CH(OSO3Na)(CH2)11CH3, 10-Eicosyl sulfate CH3(CH2)8CH(OSO3Na)(CH2)9CH3, 9-Eicosyl sulfate CH3(CH2)7CH(OSO3Na)(CH2)10CH3, 8-Eicosyl sulfate CH3(CH2)6CH(OSO3Na)(CH2)11CH3, 11-Eicosyl sulfate CH3(CH2)9CH(OSO3Na)(CH2)9 Sodium 10-Ceicosyl sulfate CH3(CH2)8CH(OSO3Na)(CH2)10CH3, Sodium 9-Ceicosyl sulfate CH3(CH2)7CH(OSO3Na)(CH2)11CH3, Sodium 11-Ceicosyl sulfate CH3(CH2)9CH(OSO3Na)(CH2)10CH3, Sodium 10-Ceicosyl sulfate CH3(CH2)8CH(OSO3Na)(CH2)11CH3, Sodium 12-Ceicosyl sulfate CH3(CH2)10CH(OSO3Na)(CH2)10CH3, Sodium 11-Ceicosyl sulfate CH3(CH2)9CH(OSO3Na)(CH2)11CH3Sodium 12-tetraalkylsulfate CH3(CH2)10CH(OSO3Na)(CH2)11CH3, Sodium 2-hexyl-1-nonylsulfate [CH3(CH2)6]CH[CH3(CH2)5]CH2OSO3Na, Sodium 2-heptyl-1-nonylsulfate [CH3(CH2)6]CH[CH3(CH2)6]CH2OSO3Na, Sodium 2-hexyl-1-decylsulfate [CH3(CH2)7]CH[CH3(CH2)5]CH2OSO3Na, Sodium 2-heptyl-1-decylsulfate [CH3(CH2)7]CH[CH3(CH2)6]CH2OSO3Na, Sodium 2-octyl-1-decylsulfate [CH3(CH2)7]CH[CH3( Sodium 2-hexyl-1-undecyl sulfate [CH3(CH2)8]CH[CH3(CH2)5]CH2OSO3Na, sodium 2-heptyl-1-undecyl sulfate [CH3(CH2)8]CH[CH3(CH2)6]CH2OSO3Na, sodium 2-octyl-1-undecyl sulfate [CH3(CH2)8]CH[CH3(CH2)7]CH2OSO3Na, sodium 2-hexyl-1-dodecyl sulfate [CH3(CH2)9]CH[CH3(CH2)5]CH2OSO3Na, or sodium 2-heptyl-1-dodecyl sulfate [CH3(CH2)9]CH[CH3(CH2)6]CH2OSO3Na. In some specific embodiments, the butterfly depression inhibitor may also be a potassium salt or ammonium salt of the above-mentioned branched alkyl sulfates or a mixture thereof.

[0031] Preferably, the mass percentage of the butterfly indentation inhibitor is 0.001% to 1%, which 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 more preferably 0.01% to 0.2%.

[0032] The chemical mechanical polishing slurry for low-recessed silicon via copper films of the present invention includes a corrosion inhibitor. In some specific embodiments, the corrosion inhibitor includes compounds having the structure of Formula 3 and / or heteroaromatic compounds containing nitrogen atoms; Formula 3 [;] [ ]

[0033] 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, or C17), R4 and R5 are each independently -H, -CH3, -CH2CH3, or -CH2CH2OH, and m is 2 or 3.

[0034] Formula 3 is an N-acetylated diamine compound, with one end being an acetylated alkyl group and the other end being an amino group or a substituted amino group, which are connected to each other through an ethylene or propylene group. The long-chain alkyl group must have more than 7 carbon atoms and no more than 17 to achieve improved 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 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.

[0035] In some specific embodiments, the corrosion inhibitor having the structure of Formula 3 may be one or more of the following: N-(3-aminopropyl)dodecanoylamine, N-(3-aminopropyl)octylamine, octylaminopropyl dimethyl tertiary amine, decaaminopropyl dimethyl tertiary amine, N-[2-(2-hydroxyethylamino)ethyl]dodecanoylamine, palmitamide propyl diethylamine, myristamide propyl dimethylamine, N-[2-(diethylamino)ethyl]stearylamine, stearamide propyl dimethylamine, stearamide ethyl diethylamine, N-octadecylamide ethylenediamine, and laurylamide propyl dimethylamine.

[0036] 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 embodiments, 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-aminotetrazole, 2-methyl-5-aminotetrazole, 1-aminotetrazole, imidazole, benzimidazole, 2-aminoimidazolium, pyrazole, 2-carboxypyrazole, and 3-aminopyrazole.

[0037] 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%, preferably 0.01% to 0.5%.

[0038] The chemical mechanical polishing slurry for low-recessed silicon through-hole copper films of this invention comprises abrasive particles. In some specific embodiments, the abrasive particles include, but are not limited to, one or more of SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3 or products formed therefrom, soft abrasive particles based on organic polymers, and particles surface-modified with silane coupling agents. The soft abrasive particles based on organic polymers include one or more of polyethylene, polytetrafluoroethylene, polyurethane, polyacrylic acid, polymethacrylic acid, polyacrylate, polymethyl methacrylate, polypropylene, polybutadiene, and other common polymer abrasive particles that can be used for chemical mechanical polishing. This invention 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 invention does not have special requirements for the shape of the abrasive particles. In some specific embodiments, 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 30~150 nm. In some specific embodiments, the abrasive particles include one or more of SiO2, Al2O3, and CeO2, and the particle size of the abrasive particles is 30~150 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%, or 20%, preferably from 0.02% to 2%.

[0039] The chemical mechanical polishing slurry for low-recessed silicon through-hole copper films of the present invention includes an oxidizing agent. In some specific embodiments, 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, perbromite, hypoiodic acid, hypoiodide, iodic acid, iodate, periodic acid, periodate, chromic acid, chromate, iron salts, copper salts, ferricyanide, and molybdates. In some specific embodiments, 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%.

[0040] The chemical mechanical polishing slurry for low-recessed silicon through-hole copper films of the present invention includes a chelating agent. In some specific embodiments, the chelating agent includes one or more amino acids and amino acid derivatives.

[0041] In some specific embodiments, the chelating agent includes one or more of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, proline, serine, threonine, tyrosine, glutamic acid, aspartic acid, glutamic acid, aspartic acid, tryptophan, histamine, arginine, lysine, methionine, cysteine, and iminodiacetic acid. The chelating agent has a mass percentage content of 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%.

[0042] In some specific embodiments, the low-recessed silicon through-hole copper film chemical mechanical polishing slurry further includes one or more of a pH adjuster, a surfactant, and a bactericide.

[0043] The chemical mechanical polishing slurry for low-recessed silicon-through-hole copper films of the present invention further includes a pH adjuster. In some specific embodiments, 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, and sulfuric acid, and the organic acid is selected from one or more of succinic acid, malonic acid, tartaric acid, and gluconic acid. In some specific embodiments, 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, and sodium hydroxide, and the organic base is selected from one or more of tetraalkylammonium hydroxide, ethanolamine, ethylenediamine, and diethylamine. The pH adjuster is used to adjust the chemical mechanical polishing slurry for low-recessed silicon-through-hole copper films, resulting in a pH value of 5 to 9, which can be 5, 6, 7, 7.3, 8, or 9. In some specific embodiments, the pH of the chemical mechanical polishing slurry for low-recessed silicon-through-hole copper films is 6 to 8.

[0044] The chemical mechanical polishing slurry for low-recessed silicon through-hole copper films of the present invention further includes a bactericide. In some specific embodiments, the bactericide includes, but is not limited to, 5-chloro-2-methyl-4-isothiazolin-3-one and / or 2-methyl-4-isothiazolin-3-one. The present invention does not have special requirements for the selection of bactericides.

[0045] The chemical mechanical polishing slurry for low-recessed silicon through-hole copper films of the present invention further includes a surfactant. In some specific embodiments, the surfactant is selected from one or more of alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfates, alkyl phosphates, sodium fatty alcohol polyoxyethylene ether sulfate, sarcosinate, taurine, polyacrylic acid, polyether, polyoxyethylene ether phosphate, polyethylene glycol, polyvinyl alcohol, polyvinyl butyral, cellulose, polyethyleneimine, polyvinylpyrrolidone, ethoxypropoxylated fatty alcohol, alkoxylated branched fatty alcohol, linear secondary alcohol polyoxyethylene ether, polyethylene glycol stearate, acetylation diol ethoxylate, alkyl ammonium salts, and alkylpyridinium salts. The present invention does not have special requirements for the selection of surfactants.

[0046] The present invention also provides the use of the above-mentioned low-recession silicon via copper film chemical mechanical polishing slurry for semiconductor substrates on the surface of copper plating, copper wiring or silicon via copper, including: contacting the low-recession 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 includes at least one copper surface or at least a portion of a copper-containing surface.

[0047] In some specific embodiments, 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 and SiN; and the dielectric layer includes one or more of TEOS, low-k materials and ultra-low-k materials.

[0048] The present invention is further illustrated below with reference to the embodiments. The scope of protection of the present invention is not limited to the following embodiments.

[0049] The specific components of the chemical mechanical polishing slurry for low-recessed silicon through-hole copper films in the embodiments and comparative examples of this invention are calculated based on the content of pure substances and prepared according to the formulas given in Tables 1-4, 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 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.

[0050] [Table 1] Polishing liquid SiO2 Chelating agents Corrosion inhibitors Butterfly-shaped depression Inhibitors Oxidizing agent pH Particle size / nm content / % Specific substances content / % specific substance content / % specific substance content / % Specific substances content / % Example 1 98 0.50 Glycine 7.30 Laurylaminopropyl dimethylamine 0.10 Sodium 9-heptadecyl sulfate 0.03 H2O2 2.00 7.3 Example 2 98 0.50 Glycine 7.30 Laurylaminopropyl dimethylamine 0.10 Sodium 9-heptadecyl sulfate 0.09 H2O2 2.00 7.3 Example 3 98 0.50 Glycine 7.30 Laurylaminopropyl dimethylamine 0.10 Sodium 7-tetradecyl sulfate 0.09 H2O2 2.00 7.3 Example 4 98 0.50 Glycine 7.30 Laurylaminopropyl dimethylamine 0.10 Sodium 2-hexyl-1-dodecyl sulfate 0.09 H2O2 2.00 7.3 Example 5 98 0.50 Glycine 7.30 1,2,4-Triazole 0.20 Sodium 9-heptadecyl sulfate 0.09 H2O2 2.00 7.3 Example 6 98 0.50 Glycine 7.30 benzotriazole 0.07 Sodium 9-heptadecyl sulfate 0.09 H2O2 2.00 7.3 Example 7 98 0.50 Glycine 7.30 N-(3-aminopropyl)octylamine 0.10 Sodium 9-heptadecyl sulfate 0.09 H2O2 2.00 7.3

[0051] [Table 2] Polishing liquid SiO2 Chelating agents Corrosion inhibitors Butterfly-shaped depression Inhibitors Oxidizing agent pH Particle size / nm content / % specific substance content / % Specific substances content / % specific substance content / % Specific substances content / % Example 8 98 0.50 Glycine 7.30 N-[2-(2-hydroxyethylamino)ethyl]dodecylamine 0.10 Sodium 9-heptadecyl sulfate 0.09 H2O2 2.00 7.3 Example 9 98 0.50 Glycine 7.30 Laurylaminopropyl dimethylamine 0.10 Sodium 9-heptadecyl sulfate 0.09 H2O2 2.00 7.3 1,2,4-Triazole 0.02 Example 10 98 0.50 creatine 7.30 Laurylaminopropyl dimethylamine 0.10 Sodium 9-heptadecyl sulfate 0.09 H2O2 2.00 7.3 Example 11 98 0.50 DL-alanine 7.30 Laurylaminopropyl dimethylamine 0.10 Sodium 9-heptadecyl sulfate 0.09 H2O2 2.00 7.3 Comparative Example 1 98 0.50 Glycine 7.30 none / none / H2O2 2.00 7.3 Comparative Example 2 98 0.50 Glycine 7.30 1,2,4-Triazole 0.20 none / H2O2 2.00 7.3

[0052] [Table 3] Polishing liquid SiO2 Chelating agents Corrosion inhibitors Butterfly-shaped depression inhibitor Oxidizing agent pH Particle size / nm content / % Specific substances content / % Specific substances content / % Specific substances content / % Specific substances content / % Comparative Example 3 98 0.50 Glycine 7.30 benzotriazole 0.07 none / H2O2 2.00 7.3 Comparative Example 4 98 0.50 Glycine 7.30 Laurylaminopropyl dimethylamine 0.10 none / H2O2 2.00 7.3 Comparative Example 5 98 0.50 Glycine 7.30 N-(3-aminopropyl)octylamine 0.10 none / H2O2 2.00 7.3 Comparative Example 6 98 0.50 Glycine 7.30 N-[2-(2-hydroxyethylamino)ethyl]dodecylamine 0.10 none / H2O2 2.00 7.3 Comparative Example 7 98 0.50 Glycine 7.30 Laurylaminopropyl dimethylamine 0.10 none / H2O2 2.00 7.3 1,2,4-Triazole 0.02 Comparative Example 8 98 0.50 creatine 7.30 Laurylaminopropyl dimethylamine 0.10 none / H2O2 2.00 7.3

[0053] [Table 4] Polishing liquid SiO2 Chelating agents Corrosion inhibitors Butterfly-shaped depression Inhibitors Oxidizing agent pH Particle size / nm content / % Specific substances content / % Specific substances content / % specific substance content / % Specific substances content / % Comparative Example 9 98 0.50 DL-alanine 7.30 Laurylaminopropyl dimethylamine 0.10 none / H2O2 2.00 7.3 Comparative Example 10 98 0.50 Glycine 7.30 Laurylaminopropyl dimethylamine 0.10 Sodium tetradecyl sulfate 0.09 H2O2 2.00 7.3 Comparative Example 11 98 0.50 Glycine 7.30 Laurylaminopropyl dimethylamine 0.10 Sodium heptadecanyl sulfate 0.09 H2O2 2.00 7.3

[0054] The performance of the low-recession silicon via copper film chemical mechanical polishing slurry provided in Examples 1-11 and the silicon via copper film polishing slurry provided in Comparative Examples 1-11 was tested. The test methods are as follows:

[0055] 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 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.

[0056] 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.

[0057] The butterfly-shaped indentation measuring machine is a KLA-Tencor P-17. It measures two feature patterns, 50μm×50μm and 10μm×10μm, and the height difference between the two platforms relative to the middle indentation is the indentation value.

[0058] The test results are shown in Table 5-8. [test] [1] [The effect of butterfly indentation inhibitors on copper removal rate and corrosion rate] [ ]

[0059] Comparative Examples 1-9 and Examples 1-11 of the present invention were selected to perform polishing and static corrosion tests on Cu substrates under the same conditions. The results of removal rate and corrosion rate are listed in Table 5.

[0060] [Table 5] Polishing liquid Copper removal rate (Å / min) at 2 psi (93 / 87 RPM) Copper corrosion rate at room temperature (Å / min) Copper surface condition Comparative Example 1 37116 2653 Severe surface corrosion Comparative Example 2 22055 376 metallic luster Comparative Example 3 20348 313 metallic luster Comparative Example 4 35816 56 metallic luster Comparative Example 5 36277 239 metallic luster Comparative Example 6 36008 102 metallic luster Comparative Example 7 35297 39 metallic luster Comparative Example 8 15321 31 metallic luster Comparative Example 9 24357 41 metallic luster Example 1 35359 42 metallic luster Example 2 34109 25 metallic luster Example 3 34300 32 metallic luster Example 4 34528 47 metallic luster Example 5 21703 45 metallic luster Example 6 20774 31 metallic luster Example 7 34448 35 metallic luster Example 8 34209 30 metallic luster Example 9 33814 19 metallic luster Example 10 15424 7 metallic luster Example 11 24007 11 metallic luster

[0061] As shown in Table 5, 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 included compounds with the structure of Formula 3, nitrogen-containing heteroaromatic compounds, or their compositions 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.

[0062] The polishing solution for the silicon through-hole copper film in Comparative Example 2 contained 1,2,4-triazole as a corrosion inhibitor. The difference between Example 5 and Comparative Example 2 was that Example 5 also contained sodium 9-heptadecyl sulfate as a butterfly indentation inhibitor. Compared to Comparative Example 2, Example 5 showed a slight decrease in the Cu film removal rate at 2 psi pressure, while the Cu film corrosion rate at room temperature decreased to 45 Å / min. The polishing solution for Comparative Example 3 contained benzotriazole as a corrosion inhibitor. The difference between Example 6 and Comparative Example 3 was that Example 6 also contained sodium 9-heptadecyl sulfate as a butterfly indentation inhibitor. Compared to Comparative Example 3, Example 6 showed a slight increase in the 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 contained laurylaminopropyl dimethylamine as a corrosion inhibitor. The difference between Examples 1-4 and Comparative Example 4 is that Examples 1-4 also contained sodium 9-heptadecyl sulfate, sodium 7-tetradecyl sulfate, and sodium 2-hexyl-1-dodecyl sulfate as butterfly indentation 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. Å / min; Similarly, analysis of the data from Comparative Examples 5 and 7, 6 and 8, and 7 and 9 shows that, in Cu polishing compositions using glycine as a chelating agent and compounds of Formula 3, nitrogen-containing heteroaromatic compounds, or their compositions as corrosion inhibitors, the addition of butterfly-shaped depression inhibitors of Formula 1 and / or Formula 2 slightly decreases the copper film removal rate, but still maintains a high removal rate under relatively low pressure (2 psi), while the surface corrosion phenomenon is further improved, indicating that the butterfly-shaped depression inhibitor can promote the anti-corrosion effect of the corrosion inhibitor, and the two have a synergistic effect.

[0063] 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 that Example 10-11 also added 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.

[0064] 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 synergistically resist corrosion with compounds of Formula 3 and nitrogen-containing heteroaromatic compounds, 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. [test] [2] [The effect of butterfly indentation inhibitors on copper indentation values] [ ]

[0065] Comparative Examples 4, 10-11 and 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.

[0066] [Table 6] Polishing liquid Copper indentation value (Å) on a 50μm×50μm pattern The reduction ratio of copper depression value (Å) on a 50μm×50μm pattern Copper indentation value (Å) on a 10μm × 10μm pattern The reduction ratio of copper depression value (Å) on a 10μm×10μm pattern Comparative Example 4 1394 0% 889 0% Comparative Example 11 934 -33.0% 651 -26.8% Example 1 1125 -19.3% 782 -12.0% Example 2 735 -47.3% 543 -38.9% Example 4 821 -41.1% 604 -32.1% Comparative Example 10 917 0% 653 0% Example 3 842 -8.2% 617 -5.5%

[0067] According to the results of Comparative Examples 4, 11 and 2 in Table 6, the addition of alkyl sulfates to the Cu polishing composition, which uses glycine as a chelating agent and laurylaminopropyl dimethylamine as a corrosion inhibitor, can improve the butterfly indentation value of the polished Cu structure sheet. Compared to Comparative Example 4, in Comparative Example 11, the amount of sodium heptadecanyl sulfate, a straight-chain alkyl sulfate with seventeen carbon atoms, added was 0.09 wt%. The copper depression value on the 50 μm × 50 μm pattern decreased by -33.0%, and the copper depression value on the 10 μm × 10 μm pattern decreased by -26.8%. In Example 2, the branched alkyl sulfate 9-heptadecanyl sulfate with the same number of carbon atoms, at the same amount added, showed a decrease in the copper depression value on the 50 μm × 50 μm pattern and the 10 μm × 10 μm pattern of -47.3% and -38.9%, respectively. This indicates that the branched alkyl sulfate (structure of Formula 1) can significantly enhance the suppression of copper butterfly depressions. 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 (Formula 1 and / or Formula 2 structures) with the same number of carbon atoms have a superior steric barrier effect, preventing excessive removal of the Cu film by penetrating the depressions adsorbed on the film surface during polishing.

[0068] The results of Comparative Example 10 and Example 3 yielded similar conclusions: compared to sodium tetradecyl sulfate with the same number of carbon atoms, the branched alkyl sulfate 7-tetradecyl sulfate better protected the depressions on the surface of the Cu film.

[0069] 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.

[0070] [Table 7] Polishing liquid Copper indentation value (Å) on a 50μm×50μm pattern The reduction in copper depression value (Å) on a 50μm×50μm pattern (%) Copper indentation value (Å) on a 10μm × 10μm pattern The reduction in copper depression value (Å) on a 10μm×10μm pattern (%) Comparative Example 2 1307 0% 809 0% Example 5 652 -50.1% 453 -44.0% Comparative Example 3 1331 0% 850 0% Example 6 902 -32.2% 608 -28.5% Comparative Example 5 1463 0% 949 0% Example 7 792 -45.9% 571 -39.8% Comparative Example 6 1427 0% 892 0% Example 8 788 -44.8% 562 -37.0% Comparative Example 7 1389 0% 897 0% Example 9 716 -48.5% 556 -38.0% Comparative Example 8 1093 0% 680 0% Example 10 509 -53.4% 367 -46.0% Comparative Example 9 1157 0% 712 0% Example 11 667 -42.3% 469 -34.1%

[0071] As shown in Table 7, the polishing solution of Comparative Example 2 contained 1,2,4-triazole as a corrosion inhibitor. The difference between Example 5 and Comparative Example 2 is that Example 5 also contained sodium 9-heptadecyl sulfate as a butterfly indentation inhibitor. Compared with Comparative Example 2, Example 5 showed a -50.1% reduction in copper indentation value on a 50μm × 50μm pattern and a -44.0% reduction on a 10μm × 10μm pattern. The polishing solution of Comparative Example 3 contained benzotriazole as a corrosion inhibitor. The difference between Example 6 and Comparative Example 3 is that Example 6 also contained sodium 9-heptadecyl sulfate as a butterfly indentation inhibitor. Compared with Comparative Example 3, Example 6 showed a -32.2% reduction in copper indentation value on a 50μm × 50μm pattern and a -28.5% reduction on a 10μm × 10μm pattern. Similarly, analysis of the 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 their compositions are used as corrosion inhibitors in Cu polishing compositions, the addition of butterfly depression inhibitors of Formula 1 and / or Formula 2 significantly improves the butterfly depression value of the polished Cu structure sheet.

[0072] 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 that Example 10-11 also added 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.

[0073] In summary, in Cu polishing solutions containing compounds of Formula 3, nitrogen-containing heteroaromatic compounds, or their components as corrosion inhibitors, and amino acids and their derivatives as chelating agents, the butterfly-shaped depression inhibitors of Formula 1 and / or Formula 2 can significantly enhance the inhibition of copper butterfly-shaped depressions. [test] [3] [Selectivity of polishing slurry containing butterfly indentation inhibitor;] [ ]

[0074] 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.

[0075] [Table 8] Cu:Ta Cu:TaN Cu:Ti Cu:TiN Cu:TEOS 2220 5007 1691 899 2805

[0076] 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 of polishing is highly desirable for many applications requiring high copper film removal rates, such as TSV applications.

[0077] Based on the above test results, the low-recession silicon through-hole copper film chemical mechanical polishing slurry of the present invention 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.

[0078] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or changes made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and technical concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A chemical mechanical polishing slurry for low-recessed silicon through-hole copper films, comprising: The mixture comprises abrasive particles, an oxidizing agent, a chelating agent, a corrosion inhibitor, a butterfly indentation inhibitor, and water; wherein the butterfly indentation inhibitor is selected from compounds having the structure of Formula 1 and / or Formula 2. Wherein, R1 and R2 are each independently C6 to C12 straight-chain or branched alkyl groups, and M is Na, K, or NH4; wherein, the chelating agent includes one or more amino acids and amino acid derivatives; wherein, by mass percentage, the abrasive particles in the low-recessed silicon-through-hole copper film chemical mechanical polishing slurry are 0.002~20%; the oxidant in the low-recessed silicon-through-hole copper film chemical mechanical polishing slurry is 0.1~10%; the chelating agent in the low-recessed silicon-through-hole copper film chemical mechanical polishing slurry is 0.1~15%; the corrosion inhibitor in the low-recessed silicon-through-hole copper film chemical mechanical polishing slurry is 0.005~1%; and the butterfly-shaped depression inhibitor in the low-recessed silicon-through-hole copper film chemical mechanical polishing slurry is 0.001~1%.

2. The chemical mechanical polishing slurry for low-recession silicon via copper films as described in claim 1, wherein, The butterfly-shaped depression inhibitor having a structure 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, and 1 0-Potassium icosyl sulfate, 9-Potassium icosyl sulfate, 11-Potassium icosyl sulfate, 10-Potassium icosyl sulfate, 12-Potassium icosyl sulfate, 11-Potassium icosyl sulfate, 12-Potassium icosyl sulfate, 7-Potassium tetradecyl sulfate, 8-Potassium pentadecyl sulfate, 7-Potassium pentadecyl sulfate, 8-Potassium hexadecyl sulfate, 7-Potassium hexadecyl sulfate, 9-Potassium heptadecyl sulfate, 8-Potassium heptadecyl sulfate, 7-Potassium heptadecyl sulfate, 9-Potassium octadecyl sulfate, 8-Potassium octadecyl sulfate, 7-Potassium octadecyl sulfate, 10-Potassium nonadecanyl sulfate, 9-Potassium nonadecanyl sulfate, 8- Nonadecanium sulfate, 7-nonadecanium sulfate, 10-eicosyl sulfate, 9-eicosyl sulfate, 8-eicosyl sulfate, 11-tetraalkyl sulfate, 10-tetraalkyl sulfate, 9-tetraalkyl sulfate, 11-tetraalkyl sulfate, 10-tetraalkyl sulfate, 12-trialkyl sulfate, 11-trialkyl sulfate, 12-tetraalkyl sulfate, 7-tetraalkyl sulfate, 7-tetraalkyl sulfate, 8-pentadecanium sulfate, 7-pentadecanium sulfate, 8-hexadecyl sulfate, 7-hexadecyl sulfate, 9-heptadecyl sulfate, 8-heptadecyl sulfate, 7 - Sodium heptadecanyl 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-trialkyl sulfate, sodium 11-tetradecyl sulfate, and sodium 12-tetradecyl sulfate;The butterfly-shaped depression inhibitor having the structure of Formula 2 includes: 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. One or more of the following: 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, sodium 2-hexyl-1-nonyl sulfate, sodium 2-heptyl-1-nonyl sulfate, sodium 2-hexyl-1-decyl sulfate, sodium 2-heptyl-1-decyl sulfate, sodium 2-octyl-1-undecyl sulfate, sodium 2-hexyl-1-undecyl sulfate, sodium 2-hexyl-1-dodecyl sulfate, and sodium 2-heptyl-1-dodecyl sulfate.

3. The chemical mechanical polishing slurry for low-recession silicon via copper films as described in claim 1, wherein, The corrosion inhibitor includes compounds having the structure of Formula 3 and / or heteroaromatic compounds containing nitrogen atoms; Formula 3; 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.

4. The chemical mechanical polishing slurry for low-recession silicon via copper films as described in claim 3, wherein, The corrosion inhibitor having the structure of Formula 3 includes one or more of the following: N-(3-aminopropyl)dodecanoylamine, N-(3-aminopropyl)octanoylamine, octanoylaminopropyl dimethyl tertiary amine, decaylaminopropyl dimethyl tertiary amine, N-[2-(2-hydroxyethylamino)ethyl]dodecanoylamine, palmitopropyl diethylamine, myristoylaminopropyl dimethylamine, N-[2-(diethylamino)ethyl]stearylamine, stearopropyl dimethylamine, stearopropyl ethyl diethylamine, N-octadecylaminoethyldiamine, and lauroylaminopropyl dimethylamine; The nitrogen-containing heteroaromatic compounds include 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-aminotetrazole, 2-methyl-5-aminotetrazole, 1-aminotetrazole, imidazole, benzimidazole, 2-aminoimidazolium, pyrazole, 2-carboxypyrazole, and 3-aminopyrazole.

5. The chemical mechanical polishing slurry for low-recession silicon via copper films as described in claim 1, wherein, The abrasive particles comprise one or more of the following: SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3, or products formed therefrom, soft abrasive particles based on organic polymers, and particles surface-modified with silane coupling agents; and / or, the particle size of the abrasive particles is 20-200 nm; and / or, the oxidant comprises one or more of the following: inorganic peroxides, persulfates, 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, and molybdates; and / or, the pH of the chemical mechanical polishing solution for low-recessed silicon through-hole copper films is 5-9.

6. The chemical mechanical polishing slurry for low-recession silicon via copper films as described in claim 1, wherein, The abrasive particles comprise one or more of SiO2, Al2O3, and CeO2; and / or, the particle size of the abrasive particles is 30-150 nm; and / or, the oxidant comprises one or more of hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, and sodium perchlorate; 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, glutamic acid, aspartic acid, glutamic acid, aspartic acid, tryptophan, histamine, arginine, lysine, methionine, cysteine, and iminodiacetic acid; and / or, the pH of the chemical mechanical polishing slurry for low-recessed silicon through-hole copper films is 6-8.

7. The chemical mechanical polishing slurry for low-recession silicon via copper films as described in claim 1, wherein, The chemical mechanical polishing slurry for low-recessed silicon through-hole copper films further includes one or more of a pH adjuster, a surfactant, and a bactericide.

8. The use of a low-recession via copper film chemical mechanical polishing slurry as described in any one of claims 1 to 7 on a semiconductor substrate on the surface of copper plating, copper wiring, or via copper, comprising the steps of: contacting the low-recession 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 includes at least one copper surface or at least a portion of a copper-containing surface.

9. The use as described in claim 8, wherein, 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 and SiN; and the dielectric layer includes one or more of TEOS, low-k materials and ultra-low-k materials.

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