Silicon through hole copper film chemical mechanical polishing solution and application thereof

Abstract

The invention discloses a through-silicon-via copper film chemical mechanical polishing solution and application thereof. The through-silicon-via copper film chemical mechanical polishing solution comprises a grinding material, an oxidizing agent, a chelating agent, a corrosion inhibitor and water, the mass percentage of the abrasive in the through silicon via copper film chemical mechanical polishing solution is 0.002-20%, and the abrasive is composed of a large-particle-size abrasive and a small-particle-size abrasive. And the mass ratio of the large-particle-size grinding material to the small-particle-size grinding material is (1: 4)-(3: 7). According to the chemical mechanical polishing solution for the through silicon via copper film, the abrasives with the large particle size and the small particle size are mixed according to the specific proportion, the contact area of the abrasives and the copper film layer in the polishing process is increased, and the high and adjustable copper film removal rate is achieved under the low down pressure; and by improving the corrosion inhibitor and the butterfly-shaped recess inhibitor, the copper film is rapidly removed, meanwhile, local and overall corrosion is improved, and butterfly-shaped recesses of the polished copper are reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of semiconductor devices, in particular to a chemical mechanical polishing liquid for through-silicon via copper film and application thereof. BACKGROUND

[0002] With the development of CMOS process, the feature size of the device is gradually reduced, and the circuit density becomes more complex, which makes the design and manufacturing more difficult. Moore's law has approached its physical limit, in order to solve the problem of signal delay, and meet the requirements of performance and power consumption, 3D packaging technology as the continuation of Moore's law, gradually developed. 3D packaging is to arrange the chips in the vertical direction, and to realize efficient interconnection by penetrating active circuit. Compared with the traditional 2D packaging, it has the advantages of small size, low power consumption, short signal delay, etc., and has been applied to the industrialization process of storage chips and CIS.

[0003] Through the complex process, the through-silicon via (TSV) is manufactured on the back of the chip, which is the key to realize the three-dimensional stacking between chips. The process mainly includes the following steps: 1. Efficient etching forms a large number of through holes; 2. Filling the through hole with a medium layer, an adhesion layer, a barrier layer and a metal layer; 3. Using chemical mechanical polishing (CMP) to remove the covered metal layer to realize planarization and circuit conduction. Since the depth of the through-silicon via is large, the thickness of the electroplated copper in the through-silicon via process is much larger than that of the copper interconnection line in the integrated circuit, reaching 2-10 μm, or even several tens of microns, which puts higher requirements on the polishing process of the copper film layer: not only to achieve high copper layer removal rate to improve yield and prevent local and overall corrosion, but also to maintain a relatively low dishing value to provide qualified process for subsequent barrier layer polishing.

[0004] With the continuous maturity of 3D packaging technology, the through-silicon via (TSV) technology is continuously applied by more downstream manufacturers, and higher requirements are put forward for the polishing process. Under the premise of keeping other specifications, it is expected to obtain higher copper film removal rate. However, in the design of the above chemical mechanical polishing slurry, various corrosion and dishing inhibitors need to be introduced, which inevitably causes the decrease of the removal rate of the copper film layer.

[0005] Therefore, it is an urgent problem for those skilled in the art to develop a through-silicon via copper film chemical mechanical polishing liquid that takes into account multiple performance aspects. SUMMARY

[0006] Therefore, the present application provides a chemical mechanical polishing liquid for through-silicon via copper film, which can quickly remove the copper film during polishing, effectively improve the local and overall corrosion of the metal material, and reduce the dishing of the copper after polishing.

[0007] The application provides a through silicon via copper film chemical mechanical polishing liquid, comprising: an abrasive, an oxidizing agent, a chelating agent, a corrosion inhibitor and water; The mass percentage of the abrasive in the through silicon via copper film chemical mechanical polishing liquid is 0.002-20%, and the abrasive is composed of large-particle-size abrasive and small-particle-size abrasive; the D 50 value of the large-particle-size abrasive is 70-110 nm, and the D 50 value of the small-particle-size abrasive is 30-50 nm, and the mass ratio of the large-particle-size abrasive to the small-particle-size abrasive is (1:4)-(3:7).

[0008] In some specific implementations, the corrosion inhibitor has a structure of Formula 1. ; wherein R1 is a linear alkyl group with 7-17 carbon atoms, R2 and R3 are each independently -H, -CH3, -CH2CH3 or -CH2CH2OH, and m is 2 or 3.

[0009] In some specific implementations, the corrosion inhibitor comprises one or more of N-(3-aminopropyl)dodecanamide, N-(3-aminopropyl)octanamide, octanamidopropyl dimethyl tertiary amine, decanamidopropyl dimethyl tertiary amine, N-[2-(2-hydroxyethylamino)ethyl]dodecanamide, palmitamidopropyl diethyl amine, myristamidopropyl dimethyl amine, N-[2-(diethylamino)ethyl]stearamide, stearamidopropyl dimethyl amine, stearamide ethyl diethyl amine, N-stearylethylenediamine or lauramidopropyl dimethyl amine.

[0010] In some specific implementations, the abrasive comprises one or more of SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3 and co-formed products thereof, soft abrasives based on organic polymers, and silane coupling agent surface modified particles. and / or, the D 50 value of the large-particle-size abrasive is 80-110 nm, and the D 50 value of the small-particle-size abrasive is 30-50 nm. and / or, the oxidizing agent comprises one or more of inorganic peroxides, persulfides, organic peroxides, hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate, hypobromous acid, hypobromite, bromic acid, bromate, perbromic acid, perbromate, hypoiodous acid, hypoiodite, iodic acid, iodate, periodic acid, periodate, chromic acid, chromate, iron salt, copper salt, ferricyanide or molybdate; and / or, the chelating agent comprises one or more of amino acids and amino acid derivatives. And / or, the pH of the through-silicon via copper film chemical mechanical polishing liquid is 5-9.

[0011] In some specific implementations, the abrasive includes one or more of SiO2, Al2O3, CeO2; And / or, the oxidizing agent includes one or more of hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, sodium perchlorate; And / or, the chelating agent includes one or more of glycine, D-alanine, L-alanine, DL-alanine, B-alanine, valine, leucine, isoleucine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine or iminodiacetic acid; And / or, the pH of the through-silicon via copper film chemical mechanical polishing liquid is 6-8.

[0012] In some specific implementations, the through-silicon via copper film chemical mechanical polishing liquid further includes a butterfly recess inhibitor, the butterfly recess inhibitor being selected from a compound of structure 2 and / or structure 3; ; In some specific implementations, the through-silicon via copper film chemical mechanical polishing liquid further includes a butterfly recess inhibitor, the butterfly recess inhibitor being selected from a compound of structure 2 and / or structure 3;

[0013] In some specific implementations, the butterfly depression inhibitor of Formula 2 includes potassium 7-tetradecyl sulfate, potassium 8-pentadecanyl sulfate, potassium 7-pentadecanyl sulfate, potassium 8-hexadecyl sulfate, potassium 7-hexadecyl sulfate, potassium 9-heptadecyl sulfate, potassium 8-heptadecyl sulfate, potassium 7-heptadecyl sulfate, potassium 9-octadecyl sulfate, potassium 8-octadecyl sulfate, potassium 7-octadecyl sulfate, potassium 10-nonadecanyl sulfate, potassium 9-nonadecanyl sulfate, potassium 8-nonadecanyl sulfate, potassium 7-nonadecanyl sulfate, potassium 10-eicosyl sulfate, potassium 9-eicosyl sulfate, potassium 8-eicosyl sulfate, potassium 11-twentiethyl sulfate, potassium 12-twentiethyl sulfate, potassium 13-twentiethyl sulfate, potassium 14-twentiethyl sulfate, potassium 15-twentiethyl sulfate, potassium 16-twentiethyl sulfate, potassium 17-twentiethyl sulfate, potassium 18-twentiethyl sulfate, potassium 19-twentiethyl sulfate, potassium 10-twentiethyl sulfate, potassium 19-twentiethyl sulfate, potassium 10-twentiethyl sulfate, potassium 19-twentiethyl sulfate, potassium 11-twentiethyl sulfate, potassium 12-twentiethyl sulfate, potassium 13-twentiethyl sulfate, potassium 14-twentiethyl sulfate, potassium 15-twentiethyl sulfate, potassium 16-twentiethyl sulfate, potassium 17-twentiethyl sulfate, potassium 18-twentiethyl sulfate, potassium 19-twentiethyl sulfate, potassium 11-twentiethyl sulfate, potassium 12-twentiethyl sulfate, potassium 13-twentiethyl sulfate, potassium 14-twentiethyl sulfate Alkyl sulfate, 10-monoalkyl sulfate, 9-monoalkyl sulfate, 11-monoalkyl sulfate, 10-monoalkyl sulfate, 12-trialkyl sulfate, 11-trialkyl sulfate, 12-tetraalkyl sulfate, 7-tetradecyl ammonium sulfate, 8-pentadecanyl ammonium sulfate, 7-pentadecanyl ammonium sulfate, 8-hexadecyl ammonium sulfate, 7-hexadecyl ammonium sulfate, 9-heptadecyl ammonium sulfate, 8-heptadecyl ammonium sulfate, 7-heptadecyl ammonium sulfate, 9-octadecyl ammonium sulfate, 8-octadecyl ammonium sulfate, 7-octadecyl ammonium sulfate, 10-nonadecanyl ammonium sulfate, 9-nonadecanyl sulfate Ammonium sulfate, 8-nonadecanoylammonium sulfate, 7-nonadecanoylammonium sulfate, 10-eicosylammonium sulfate, 9-eicosylammonium sulfate, 8-eicosylammonium sulfate, 11-tetraalkylammonium sulfate, 10-tetraalkylammonium sulfate, 9-tetraalkylammonium sulfate, 11-tetraalkylammonium sulfate, 10-tetraalkylammonium sulfate, 12-trialkylammonium sulfate, 11-trialkylammonium sulfate, 12-tetraalkylammonium sulfate, 7-tetraalkylammonium sulfate, 7-tetraalkylammonium sulfate, 8-pentadecanoylammonium sulfate, 7-pentadecanoylammonium sulfate, 8-hexadecylammonium sulfate, 7-hexadecylammonium sulfate, 9-heptadecylammonium sulfate, 8-heptadecylsulfonium sulfate Sodium sulfate, sodium 7-heptadecyl sulfate, sodium 9-octadecyl sulfate, sodium 8-octadecyl sulfate, sodium 7-octadecyl sulfate, sodium 10-nonadecanyl sulfate, sodium 9-nonadecanyl sulfate, sodium 8-nonadecanyl sulfate, sodium 7-nonadecanyl sulfate, sodium 10-eicosyl sulfate, sodium 9-eicosyl sulfate, sodium 8-eicosyl sulfate, sodium 11-tetradecyl sulfate, sodium 10-tetradecyl sulfate, sodium 9-tetradecyl sulfate, sodium 11-tetradecyl sulfate, sodium 10-tetradecyl sulfate, sodium 12-tridecyl sulfate, sodium 11-tetradecyl sulfate, or sodium 12-tetradecyl sulfate; The butterfly-shaped recess inhibitor of the structure of formula 3 includes one or more of 2-hexyl-1-nonyl potassium sulfate, 2-heptyl-1-nonyl potassium sulfate, 2-hexyl-1-decyl potassium sulfate, 2-heptyl-1-decyl potassium sulfate, 2-octyl-1-decyl potassium sulfate, 2-hexyl-1-undecyl potassium sulfate, 2-heptyl-1-undecyl potassium sulfate, 2-octyl-1-undecyl potassium sulfate, 2-hexyl-1-dodecyl potassium sulfate, 2-heptyl-1-dodecyl potassium sulfate, 2-hexyl-1-nonyl ammonium sulfate, 2-heptyl-1-nonyl ammonium sulfate, 2-hexyl-1-decyl ammonium sulfate, 2-heptyl-1-decyl ammonium sulfate, 2-octyl-1-decyl ammonium sulfate, 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 sodium sulfate, 2-heptyl-1-nonyl sodium sulfate, 2-hexyl-1-decyl sodium sulfate, 2-heptyl-1-decyl sodium sulfate, 2-octyl-1-decyl sodium sulfate, 2-hexyl-1-undecyl sodium sulfate, 2-heptyl-1-undecyl sodium sulfate, 2-octyl-1-undecyl sodium sulfate, 2-hexyl-1-dodecyl sodium sulfate, or 2-heptyl-1-dodecyl sodium sulfate.

[0014] In some specific implementations, the mass percentage content of the butterfly-shaped recess inhibitor in the polishing liquid is 0.001-1%.

[0015] In some specific implementations, the through-silicon via copper film chemical mechanical polishing liquid further includes one or more of a pH adjuster, a surfactant, and a bactericide.

[0016] In some specific implementations, the mass percentage content of the abrasive in the through-silicon via copper film chemical mechanical polishing liquid is 0.02-2% by mass percentage; and / or, the mass percentage content of the oxidizing agent in the through-silicon via copper film chemical mechanical polishing liquid is 0.1-10%; and / or, the mass percentage content of the chelating agent in the through-silicon via copper film chemical mechanical polishing liquid is 0.1-15%; and / or, the mass percentage content of the corrosion inhibitor in the through-silicon via copper film chemical mechanical polishing liquid is 0.005-1%.

[0017] The application also provides an application of the through-silicon via copper film chemical mechanical polishing liquid as described above to a semiconductor substrate with a copper plating film, a copper wiring, or a surface of a through-silicon via copper, including: contacting the through-silicon via copper film chemical mechanical polishing liquid with the semiconductor substrate to be polished and performing chemical mechanical polishing processing; and the surface to be polished of the semiconductor substrate contains at least one copper or copper-containing surface.

[0018] In some specific implementations, the semiconductor substrate to be polished further comprises a barrier layer and / or a dielectric layer, the barrier layer comprising one or more of Ta, TaN, Ti, TiN or SiN; the dielectric layer comprising one or more of TEOS, low-k or ultra-low-k.

[0019] The application provides a chemical mechanical polishing solution for polishing a through-silicon via (TSV) copper film. By mixing abrasive materials of two sizes in a specific ratio, the contact area between the abrasive material and the copper film layer during polishing can be increased, thereby increasing the removal rate of copper. A high and adjustable copper film removal rate can be achieved under low down pressure (the removal rate of copper can be more than 38000 A / min under a low down pressure of 2 psi), significantly improving production efficiency. By adding a new corrosion inhibitor, local and overall corrosion of metal materials can be effectively inhibited (the copper corrosion rate is reduced to 31 A / min) while achieving a high polishing rate, thereby improving product yield. By adding a new butterfly recess inhibitor, the butterfly recess can be kept low (the copper butterfly recess value is as low as 407 A) during high-speed copper film removal, and the corrosion condition can be further improved, laying a good foundation for subsequent barrier layer polishing. In addition, the CMP composition has excellent polishing selectivity and can achieve high selective removal of copper film relative to barrier layer (such as Ta, TaN, Ti, TiN or SiN) and dielectric layer (such as TEOS, low-k or ultra-low-k). DETAILED DESCRIPTION

[0020] It should be understood that the expression "one or more of A and / or B" includes each of the objects recited after the expression and various combinations of two or more of the recited objects, individually, unless otherwise understood from the context and usage. The expression "and / or" in combination with three or more recited objects should be understood to have the same meaning, unless otherwise understood from the context.

[0021] The use of the expressions "including", "having" or "containing", including the use of their grammatical synonyms, should generally be understood to be open-ended and non-limiting, for example, not excluding other unrecited elements or steps, unless otherwise specifically stated or understood from the context.

[0022] It should be understood that the order of steps or order for performing certain actions is immaterial so long as the application remains operable. Moreover, two or more steps or actions can be conducted simultaneously.

[0023] The use of any and all examples, or exemplary language herein, for example, "such as" or "including", is intended merely to better illustrate the application and does not pose a limitation on the scope of the application unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the application.

[0024] Further, to the extent that any numerical ranges are stated to include endpoint values, the endpoint values are appropriately inclusive of the precision of the measurement, rounding up to the nearest significant figure. Further, any numerical range can be inclusive or exclusive. Furthermore, all ranges disclosed herein are understood to be inclusive of the endpoints and independently combinable. For example, a range of 2 to 10 can include 2, 3, 4, 5, 6, 7, 8, 9, 10, 2.1, 2.8, 3.5, 4.2, 4.9, 5.6, 6.3, 7.0, 7.7, 8.4, 9.1, and 9.8 etc.

[0025] The application provides a through silicon via copper film chemical mechanical polishing liquid, comprising: abrasive, oxidizing agent, chelating agent, corrosion inhibitor and water. The mass percentage of the abrasive in the through silicon via copper film chemical mechanical polishing liquid is 0.002-20%, which is composed of large-particle-size abrasive and small-particle-size abrasive; the D 50 value of the large-particle-size abrasive is 70-110 nm, and the D 50 value of the small-particle-size abrasive is 30-50 nm; and the mass ratio of the large-particle-size abrasive to the small-particle-size abrasive is (1:4)-(3:7).

[0026] In some specific implementations, the abrasive includes, but is not limited to, one or more of SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3, a co-formed product thereof, a soft abrasive particle based on an organic polymer, or a particle surface-modified by a silane coupling agent. The soft abrasive particle based on an organic polymer includes one or more of polyethylene, polytetrafluoroethylene, polyurethane, polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, polypropylene, polybutadiene, and common polymer abrasives used in chemical mechanical polishing. The application does not have special requirements for the selection of the abrasive. The abrasive can have different shapes, including spherical, cocoon-shaped, string-shaped, curved, and various other shapes, and the application does not have special requirements for the shape of the abrasive particle.

[0027] In some specific implementations, the mass percentage of the abrasive can be 0.002%, 0.005%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.1%, 0.5%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 5%, 10%, 15%, 18%, 20%, preferably 0.02%-2%. In some specific implementations, the D 50 value of the large-particle-size abrasive can be 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 105 nm, 110 nm, preferably 80-110 nm; and the D 50The value can be 30 nm, 35 nm, 40 nm, 45 nm, 50 nm; the mass ratio of the large particle size abrasive to the small particle size abrasive can be 1:4, 2:7, 3:10, 1:3, 3:8, 2:5, 3:7.

[0028] The chemical mechanical polishing liquid for through silicon via copper film described in the present application comprises a corrosion inhibitor. In some specific implementations, the corrosion inhibitor has the structure of Formula 1. ; wherein R1 is a linear alkyl group of C7 to C17 (may be C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17), R2 and R3 are each independently -H, -CH3, -CH2CH3 or -CH2CH2OH, and m is 2 or 3.

[0029] Formula 1 is an N-acyl diamine compound, one end of which is an amide with a long-chain alkyl group, and the other end is an amino or substituted amino group, both of which are connected to each other through an ethylene or propylene group. The number of carbons in the long-chain alkyl group is greater than 7 and cannot be greater than 17, which can achieve the effect of improving local and overall corrosion, because too long a chain length will cause too many carbon atoms, resulting in poor corrosion resistance. The corrosion inhibitor of Formula 1 can effectively reduce the local and overall corrosion of copper, and the copper surface can maintain the original metal luster, while in the polishing process, under the action of shear force, it constantly separates and recombines on the surface of the copper in a "dynamic" form, thereby maintaining a high copper removal rate.

[0030] In some specific implementations, the corrosion inhibitor includes, but is not limited to, one or more of N-(3-aminopropyl)dodecanamide, N-(3-aminopropyl)octanamide, octanamide propyl dimethyl tertiary amine, decanamide propyl dimethyl tertiary amine, N-[2-(2-hydroxyethylamino)ethyl]dodecanamide, palmitamide propyl diethyl amine, myristamide propyl dimethyl amine, N-[2-(diethylamino)ethyl]stearic amide, stearic amide propyl dimethyl amine, stearic amide ethyl diethyl amine, N-octadecanoyl ethylenediamine, lauramide propyl dimethyl amine.

[0031] The mass percentage content of the corrosion inhibitor is 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%, 1%, and is preferably 0.01% to 0.5%.

[0032] The through-silicon via copper film chemical mechanical polishing solution described in the present application comprises an oxidizing agent. In some specific implementations, the oxidizing agent comprises one or more of inorganic peroxide, persulfide, organic peroxide, hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate, hypobromous acid, hypobromite, bromic acid, bromate, perbromic acid, perbromate, hypoiodous acid, hypoiodite, iodic acid, iodate, periodic acid, periodate, chromic acid, chromate, ferrite, copper salt, ferricyanide, or molybdate. In some specific implementations, the oxidizing agent comprises one or more of hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, sodium perchlorate. The oxidizing agent is used to oxidize the metal copper film into a mixture of copper oxides to allow it to react quickly with the chelating agent. The mass percentage of the oxidizing agent is 0.1% to 10%, which can be 0.1%, 0.2%, 0.3%, 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.5%, 10%, preferably 0.5-5%.

[0033] The through-silicon via copper film chemical mechanical polishing solution described in the present application comprises a chelating agent. In some specific implementations, the chelating agent comprises one or more of amino acids, amino acid derivatives. In some specific implementations, the chelating agent comprises but is not limited to one or more of glycine, D-alanine, L-alanine, DL-alanine, B-alanine, valine, leucine, isoleucine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, or iminodiacetic acid. The present application does not have special requirements for the selection of chelating agents, and glycine is preferred. The mass percentage of the chelating agent is 0.1% to 15%, which can be 0.1%, 0.2%, 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.5%, 10%, 15%, preferably 0.5% to 10%.

[0034] The through-silicon via copper film chemical mechanical polishing solution provided in the present application can also comprise a butterfly recess inhibitor selected from the compounds of structure 2 and / or structure 3; ; wherein R4, R5 are each independently C6 to C12 linear or branched alkyl, and M is Na, K, or NH4.

[0035] When the alkyl chain is too short or too long, the "protection" effect of the selected branched alkyl sulfate on the Cu surface during the chemical mechanical polishing process is reduced. When the alkyl chain is too short, the hydrophobic part of the molecule fails to well isolate the attack of the chemical substances on the copper film layer, and when the alkyl chain is too long, the adsorption of the molecule on the Cu surface will be reduced, both of which will lead to the "incompleteness" of the protective film layer.

[0036] Preferably, the butterfly-shaped depression suppressor of structure of Formula 2 includes one or more of 7-tetradecyl potassium sulfate, 8-pentadecyl potassium sulfate, 7-pentadecyl potassium sulfate, 8-hexadecyl potassium sulfate, 7-hexadecyl potassium sulfate, 9-heptadecyl potassium sulfate, 8-heptadecyl potassium sulfate, 7-heptadecyl potassium sulfate, 9-octadecyl potassium sulfate, 8-octadecyl potassium sulfate, 7-octadecyl potassium sulfate, 10-nonadecyl potassium sulfate, 9-nonadecyl potassium sulfate, 8-nonadecyl potassium sulfate, 7-nonadecyl potassium sulfate, 10-icosyl potassium sulfate, 9-icosyl potassium sulfate, 8-icosyl potassium sulfate, 11-heneicosyl potassium sulfate, 10-heneicosyl potassium sulfate, 9-heneicosyl potassium sulfate, 11-docosyl potassium sulfate, 10-docosyl potassium sulfate, 12-tricosyl potassium sulfate, 11-tricosyl potassium sulfate, 12-tetracosyl potassium sulfate, 7-tetradecyl ammonium sulfate, 8-pentadecyl ammonium sulfate, 7-pentadecyl 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-nonadecyl ammonium sulfate, 9-nonadecyl ammonium sulfate, 8-nonadecyl ammonium sulfate, 7-nonadecyl ammonium sulfate, 10-icosyl ammonium sulfate, 9-icosyl ammonium sulfate, 8-icosyl ammonium sulfate, 11-heneicosyl ammonium sulfate, 10-heneicosyl ammonium sulfate, 9-heneicosyl ammonium sulfate, 11-docosyl ammonium sulfate, 10-docosyl ammonium sulfate, 12-tricosyl ammonium sulfate, 11-tricosyl ammonium sulfate, 12-tetracosyl ammonium sulfate, 7-tetradecyl sodium sulfate, 8-pentadecyl sodium sulfate, 7-pentadecyl sodium sulfate, 8-hexadecyl sodium sulfate, 7-hexadecyl sodium sulfate, 9-heptadecyl sodium sulfate, 8-heptadecyl sodium sulfate, 7-heptadecyl sodium sulfate, 9-octadecyl sodium sulfate, 8-octadecyl sodium sulfate, 7-octadecyl sodium sulfate, 10-nonadecyl sodium sulfate, 9-nonadecyl sodium sulfate, 8-nonadecyl sodium sulfate, 7-nonadecyl sodium sulfate, 10-icosyl sodium sulfate, 9-icosyl sodium sulfate, 8-icosyl sodium sulfate, 11-heneicosyl sodium sulfate, 10-heneicosyl sodium sulfate, 9-heneicosyl sodium sulfate, 11-docosyl sodium sulfate, 10-docosyl sodium sulfate, 12-tricosyl sodium sulfate, 11-tricosyl sodium sulfate, or 12-tetracosyl sodium sulfate.

[0037] Preferably, the butterfly dimple suppressor of the structure of Formula 3 includes one or more of 2-hexyl-1-nonyl potassium sulfate, 2-heptyl-1-nonyl potassium sulfate, 2-hexyl-1-decyl potassium sulfate, 2-heptyl-1-decyl potassium sulfate, 2-octyl-1-decyl potassium sulfate, 2-hexyl-1-undecyl potassium sulfate, 2-heptyl-1-undecyl potassium sulfate, 2-octyl-1-undecyl potassium sulfate, 2-hexyl-1-dodecyl potassium sulfate, 2-heptyl-1-dodecyl potassium sulfate, 2-hexyl-1-nonyl ammonium sulfate, 2-heptyl-1-nonyl ammonium sulfate, 2-hexyl-1-decyl ammonium sulfate, 2-heptyl-1-decyl ammonium sulfate, 2-octyl-1-decyl ammonium sulfate, 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 sodium sulfate, 2-heptyl-1-nonyl sodium sulfate, 2-hexyl-1-decyl sodium sulfate, 2-heptyl-1-decyl sodium sulfate, 2-octyl-1-decyl sodium sulfate, 2-hexyl-1-undecyl sodium sulfate, 2-heptyl-1-undecyl sodium sulfate, 2-octyl-1-undecyl sodium sulfate, 2-hexyl-1-dodecyl sodium sulfate, or 2-heptyl-1-dodecyl sodium sulfate.

[0038] The butterfly dimple suppressor provided in the present application has two C6-C12 hydrophobic alkyl chains, which can isolate the attack of chemical substances on the copper film layer, has more excellent steric hindrance than a straight-chain alkyl sulfate with the same number of carbon atoms, can synergistically act with a corrosion inhibitor to further reduce the copper corrosion rate, thereby improving product yield. Meanwhile, the butterfly dimple suppressor protects the copper film layer surface in the trench from being excessively removed within the over-throw time by being adsorbed on the surface, thereby significantly improving the butterfly dimple after polishing. Since it is also adsorbed on the copper layer surface at a high step, the removal rate of the copper film as a whole has a small decrease, but a high and adjustable copper removal rate can still be achieved at a lower down pressure, thereby guaranteeing production efficiency.

[0039] In some specific implementations, the butterfly dimple suppressor can be 7-tetradecyl sodium sulfate , 8-pentadecyl sodium sulfate , 7-pentadecyl sodium sulfate , 8-hexadecyl sodium sulfate , 7-hexadecyl sodium sulfate , 9-heptadecyl sodium sulfate , 8-heptadecyl sodium sulfate , 7-heptadecyl sodium sulfate , 9-octadecyl sodium sulfate , 8-octadecyl sodium sulfate , 7-octadecyl sodium sulfate , 10-nonyl sodium sulfate , 9-nonyl sodium sulfate , 8-nonyl sodium sulfate , 7-nonyl sodium sulfate , 10-eicosyl sodium sulfate , 9-eicosyl sodium sulfate , 8-eicosyl sodium sulfate , 11-uncosyl sodium sulfate , 10-uncosyl sodium sulfate , 9-uncosyl sodium sulfate , 11-docosyl sodium sulfate , 10-docosyl sodium sulfate , 12-tricosyl sodium sulfate , 11-tricosyl sodium sulfate , 12-tetracosyl sodium sulfate , 2-hexyl-1-nonyl sodium sulfate , 2-heptyl-1-nonyl sodium sulfate , 2-hexyl-1-decyl sodium sulfate , 2-heptyl-1-decyl sodium sulfate , 2-octyl-1-decyl sodium sulfate , 2-hexyl-1-undecyl sodium sulfate , 2-heptyl-1-undecyl sodium sulfate , 2-octyl-1-undecyl sodium sulfate , 2-hexyl-1-dodecyl sodium sulfate , 2-heptyl-1-dodecyl sodium sulfate In some specific implementations, the bowing inhibitor can also be potassium salts or ammonium salts of the branched alkyl sulfates described above, and mixtures thereof.

[0040] Preferably, the bowing inhibitor has a mass percentage content of 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%, 1%, preferably 0.01% to 0.2%.

[0041] In some specific implementations, the through-silicon via copper film chemical mechanical polishing liquid further comprises one or more of a pH adjuster, a surfactant, and a bactericide.

[0042] The through-silicon via copper film chemical mechanical polishing solution described in the present application further comprises a pH adjuster. In some specific implementations, the pH adjuster is an acid adjuster selected from one or more of an organic acid or an inorganic acid, the inorganic acid being selected from one or more of hydrochloric acid, phosphoric acid, nitric acid or sulfuric acid, and the organic acid being selected from one or more of succinic acid, malonic acid, tartaric acid or gluconic acid. In some specific implementations, the pH adjuster is a base adjuster selected from one or more of an inorganic base or an organic base, the inorganic base being selected from one or more of ammonium hydroxide, potassium hydroxide or sodium hydroxide, and the organic base being selected from one or more of tetraalkylammonium hydroxide, ethanolamine, ethylenediamine or diethylamine. The pH of the through-silicon via copper film chemical mechanical polishing solution is adjusted using the pH adjuster, and the pH of the through-silicon via copper film chemical mechanical polishing solution is 5 to 9, which can be 5, 6, 7, 7.3, 8 or 9. In some specific implementations, the pH of the through-silicon via copper film chemical mechanical polishing solution is 6 to 8.

[0043] The through-silicon via copper film chemical mechanical polishing solution described in the present application further comprises 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, and the present application does not have special requirements for the selection of the bactericide.

[0044] The through-silicon via copper film chemical mechanical polishing solution described in the present application further comprises a surfactant. In some specific implementations, the surfactant is selected from one or more of an alkyl sulfonate, an alkyl benzene sulfonate, an alkyl sulfate, an alkyl phosphate, a fatty alcohol polyoxyethylene ether sodium sulfate, a sarcosinate, a taurinate, a polyacrylic acid, a polyether, a polyoxyethylene ether phosphate, a polyethylene glycol, a polyvinyl alcohol, a polyvinyl butyral, a cellulose, a polyethylene imine, a polyvinyl pyrrolidone, an ethoxy propoxy fatty alcohol, an alkoxylated branched fatty alcohol, a linear secondary alcohol polyoxyethylene ether, a polyethylene glycol stearate, an acetylenic diol ethoxylate, an alkyl ammonium salt or an alkyl pyridinium salt, and the present application does not have special requirements for the selection of the surfactant.

[0045] The present application also provides an application of the above-mentioned through-silicon via copper film chemical mechanical polishing solution, which is used for the surface of a copper plated film, a copper wiring or a through-silicon via copper of a semiconductor substrate, and comprises: contacting the through-silicon via copper film chemical mechanical polishing solution with a semiconductor substrate to be polished and performing a chemical mechanical polishing process; and the surface to be polished of the semiconductor substrate comprises at least one copper or copper-containing surface.

[0046] In some specific implementations, the semiconductor substrate to be polished further comprises a barrier layer and / or a dielectric layer, the barrier layer comprising one or more of Ta, TaN, Ti, TiN or SiN, and the dielectric layer comprising one or more of TEOS, low-k or ultra-low-k. The application will be further described in conjunction with the examples. The protection scope of the application is not limited by the following examples.

[0047] The specific components of the through silicon via copper film chemical mechanical polishing solution in the examples and comparative examples of the application are calculated according to the content of pure substance, and are prepared according to the formula given in Tables 1-2, with the balance being water (the content % in the table represents mass percent), the various components are mixed uniformly, then nitric acid or potassium hydroxide is used to adjust the pH to the required value, and then mixed uniformly to prepare the through silicon via copper film chemical mechanical polishing solution. The content of each component of the through silicon via copper film chemical mechanical polishing solution is the concentration actually used in the polishing process, and commercially available products can be appropriately concentrated.

[0048] Table 1

[0049] Table 2

[0050] The through silicon via copper film chemical mechanical polishing solutions provided in Examples 1-7 and the through silicon via copper film polishing solutions provided in Comparative Examples 1-6 were subjected to performance testing, and the testing method was as follows: The samples to be polished were polished; the samples to be polished were 8-inch copper (Cu) wafer blanks and 8-inch copper wafer 854 structure pieces, 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 uniform polishing time for the blanks was 1 min, and the 854 structure pieces were polished until no copper film remained. The polishing was performed using a polishing machine model SIZONE TENMS-200 Plus, a polishing pad model IC1010, a polishing head and polishing disc rotation speed of 93 rpm and 87 rpm, respectively, and a polishing solution flow rate of 150 ml / min.

[0051] The metal film thickness measurement machine was NAPSON RG3000, which measured the film thickness change value before and after polishing using 49 points, thereby calculating the polishing rate. The dielectric film thickness measurement machine was FILMETRICS F54-XYT-300, which also measured the film thickness change value before and after polishing using 49 points, thereby calculating the polishing rate.

[0052] The butterfly-shaped recess measurement machine was KLA-Tencor P-17, which measured two characteristic patterns of 50umx50um and 10umx10um, and the height difference between the two platforms relative to the middle recess, i.e. the recess value.

[0053] Comparative Examples 1-6 and Example 1-7 were selected to polish Cu substrate and Cu structure under the same conditions, and static corrosion test was performed on the Cu substrate. The results of removal rate, corrosion rate and dishing value are shown in Table 3.

[0054] Table 3

[0055] As shown by the results of Comparative Examples 1-3 in Table 3, in the Cu polishing composition selected with glycine as the chelating agent and lauryl amido propyl dimethyl amine as the corrosion inhibitor, the copper film removal rate and the dishing value both increased with the increase of the abrasive particle size. When the silicon particle size increased from 41 nm to 103 nm, the copper film removal rate under 2 psi pressure increased by 10.5%, and the copper dishing values on the 50 um x 50 um and 10 um x 10 um patterns increased by 30.3% and 18.9%, respectively. Comparative Examples 4-5 and Example 1 mixed the two sizes of silica sol in a specific ratio and then polished the copper film, while keeping the proportion of abrasives in the polishing liquid unchanged. As can be seen from the results, when the proportion of large particle size abrasives in the total amount of abrasives was 24% (the mass ratio of large particle size abrasives to small particle size abrasives was 6:19) (Example 1), the copper film removal rate reached the maximum value, which was 18.1% and 6.9% higher than that when only small particle size or large particle size abrasives existed (Comparative Example 1, Comparative Example 3), respectively, and the copper dishing values on the 50 um x 50 um and 10 um x 10 um patterns did not change significantly. The above results show that the two sizes of abrasives have a synergistic effect on the improvement of the copper removal rate. It is speculated that mixing the two sizes of silica sol in a specific ratio can increase the contact area between the abrasives and the copper film layer during polishing, thereby improving the copper removal rate. However, since the proportion of large particle size abrasives is not high, the dishing value at the feature pattern does not change significantly. In Comparative Example 4, the proportion of large particle size abrasives in the total amount of abrasives was 10% (the mass ratio of large particle size abrasives to small particle size abrasives was 1:9), and the copper film removal rate increased limitedly. When the proportion of large particle size abrasives further increased to 40% (Comparative Example 5, the mass ratio of large particle size abrasives to small particle size abrasives was 2:3), the dishing value at the feature pattern increased significantly. In Example 2, the two sizes of silica sol were mixed in a specific ratio (the mass ratio of large particle size abrasives to small particle size abrasives was 6:19) and then used to polish the copper film, and the results were similar. The copper film removal rate was 15.8% and 6.8% higher than that when only small particle size or large particle size abrasives existed (Comparative Example 1, Comparative Example 3), respectively, and the copper dishing values on the 50 um x 50 um and 10 um x 10 um patterns did not change significantly. The above results show that the two different sizes of abrasives can only be mixed in a specific mass ratio of (1:4) to (3:7) to maintain a high copper removal rate while keeping a low dishing value.

[0056] As shown in the results of Comparative Example 6 and Examples 1, 3-4, the polishing composition in which glycine is used as a chelating agent and two sizes of silica sols of 41 nm and 103 nm are mixed in a specific ratio, and the compound having the structure of Formula 1 provided by the present application is used as a corrosion inhibitor (Examples 1, 3-4), can maintain a high copper film layer removal rate, and the copper surface corrosion phenomenon and the recess value after polishing are effectively controlled. When a nitrogen azole compound is selected as a corrosion inhibitor (Comparative Example 6), although the copper recess value at the characteristic pattern is slightly improved, the copper film removal rate is greatly decreased, and the copper surface corrosion rate at room temperature is increased, indicating that compared with the conventional nitrogen azole corrosion inhibitor, the corrosion inhibitor provided by the present application can achieve a high and adjustable copper film removal rate under a lower down pressure, significantly improve the production efficiency, and effectively control the copper surface corrosion phenomenon and the recess value after polishing.

[0057] This is because the conventional azole corrosion inhibitor is easily combined with the copper film to form a dense molecular thin film, greatly affecting the removal rate of the copper film layer, and being not conducive to the subsequent cleaning process. The novel corrosion inhibitor of the present application can effectively reduce the local and overall corrosion of copper, and the copper surface can maintain the original metal luster, and under the action of shear force in the polishing process, it is constantly separated and recombined on the surface of copper in a "dynamic" form, thereby maintaining a high copper removal rate.

[0058] The results of Examples 5-7 show that the compound having the structure of Formula 2 or Formula 3 provided by the present application is added to the polishing composition as a butterfly-shaped recess inhibitor, the copper film layer removal rate is slightly decreased, but a high removal rate is still maintained under a relatively low down pressure, and the surface corrosion phenomenon and the recess value after polishing are further improved. Therefore, in the Cu polishing solution in which the compound having the structure of Formula 1 is used as a corrosion inhibitor and the amino acid and its derivative are used as a chelating agent, the butterfly-shaped recess inhibitor having the structure of Formula 2 or Formula 3 can significantly enhance the inhibition of copper butterfly-shaped recess, and the butterfly-shaped recess inhibitor only has a weak reducing effect on the copper removal rate, but a high removal rate is still maintained under a relatively low down pressure, and can synergistically play an anti-corrosion role with the compound having the structure of Formula 3, thereby further improving the copper surface corrosion phenomenon.

[0059] The through silicon via copper film chemical mechanical polishing solution provided in Example 5 is selected to measure the selectivity of the Cu film with respect to other barrier layers such as Ta, TaN, Ti and TiN, and dielectric films such as TEOS. The selectivity results when using a down pressure of 2 psi are listed in Table 4.

[0060] Table 4

[0061] As shown in the results in Table 4, the removal rate of the polishing composition to the Cu film is much higher than that to other substrate layer materials in the chemical mechanical polishing process, and such high selectivity of polishing is highly desirable for many applications requiring high copper film removal rate, such as TSV applications.

[0062] Based on the above test results, the through-silicon via copper film chemical mechanical polishing liquid in the present application can remove the copper film layer at a faster speed, while effectively improving the local and overall corrosion of the metal material, and reducing the butterfly-shaped depression of copper after polishing. It is worth mentioning that the concentration of each component in the above examples is the actual amount used in the polishing process, and the system can be appropriately concentrated and kept in a stable state, so as to facilitate production, transportation and use at the customer end.

[0063] The above is only the preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto, any person skilled in the art within the technical range disclosed in the present application, according to the technical scheme and the application concept of the present application, makes equivalent replacement or change, should be covered in the protection scope of the present application.

Claims

1. A through silicon via copper film chemical mechanical polishing liquid characterized by, include: Abrasives, oxidants, chelating agents, corrosion inhibitors, and water; The mass percentage of the abrasive in the through silicon via copper film chemical mechanical polishing liquid is 0.002-20%, and the abrasive is composed of large-particle abrasives and small-particle abrasives; the D 50 value of the large-particle abrasives is 70-110 nm, the D 50 value of the small-particle abrasives is 30-50 nm, and the mass ratio of the large-particle abrasives to the small-particle abrasives is (1:4)-(3:7).

2. The through silicon via copper film chemical mechanical polishing liquid according to claim 1, wherein The corrosion inhibitor has the structure of Formula 1; ； Wherein, R1 is a straight-chain alkyl group from C7 to C17, R2 and R3 are each independently -H, -CH3, -CH2CH3 or -CH2CH2OH, and m is 2 or 3.

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

4. The chemical mechanical polishing slurry for through-silicon via copper films according to claim 1, characterized in that, The abrasive includes one or more of the following: SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3 and their co-formed products, soft abrasives based on organic polymers, and particles with surface modification by silane coupling agents. and / or the D50 value of the large particle size abrasive is from 80 nm to 110 nm, the D50 value of the small particle size abrasive is from 30 nm to 50 nm. 50 and / or the D50 value of the large particle size abrasive is from 80 nm to 110 nm, the D50 value of the small particle size abrasive is from 30 nm to 50 nm. 50 and / or the D50 value of the 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; And / or, the chelating agent includes one or more amino acids and amino acid derivatives; And / or, the pH of the through-silicon via copper film chemical mechanical polishing solution is 5-9.

5. The chemical mechanical polishing slurry for through-silicon via copper films according to claim 1, characterized in that, The abrasive includes one or more of SiO2, Al2O3, and CeO2; 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, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, or iminodiacetic acid; And / or, the pH of the through-silicon via copper film chemical mechanical polishing solution is 6-8.

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

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

8. The chemical mechanical polishing slurry for through-silicon via copper films according to claim 6, characterized in that, The mass percentage of the butterfly-shaped indentation inhibitor in the polishing slurry is 0.001~1%.

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

10. The chemical mechanical polishing slurry for through-silicon via copper films according to claim 1, characterized in that, The abrasive content in the through-silicon via copper film chemical mechanical polishing slurry is 0.02% to 2% by mass. And / or, the oxidant has a mass percentage of 0.1% to 10% in the chemical mechanical polishing slurry for through-silicon via copper films; And / or, the chelating agent has a mass percentage content of 0.1% to 15% in the chemical mechanical polishing slurry for through-silicon via copper films; And / or, the corrosion inhibitor has a mass percentage content of 0.005~1% in the chemical mechanical polishing slurry for through-silicon via copper films.

11. The application of a chemical mechanical polishing slurry for through-silicon via copper films as described in any one of claims 1 to 10, characterized in that, Semiconductor substrates for copper plating, copper wiring, or through-silicon via (TSV) copper surfaces include: contacting a TSV copper film chemical mechanical polishing slurry with the semiconductor substrate to be polished and performing a chemical mechanical polishing treatment; the surface of the semiconductor substrate to be polished includes at least one copper or at least a portion of a copper-containing surface.

12. The application according to claim 11, 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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