Corrosion-resistant chemical mechanical polishing solution for through silicon via copper film and application thereof

Abstract

This application discloses a corrosion-resistant chemical mechanical polishing (CMP) slurry for through-silicon via (TSV) copper films and its application. The CMP slurry comprises abrasive particles, an oxidant, a chelating agent, a corrosion inhibitor, and water; the corrosion inhibitor has a structure of Formula 1. Applying the CMP slurry to TSV copper film polishing achieves a copper removal rate as high as 35816 Å / min under a low pressure of 2 psi, and the copper removal rate is adjustable. Simultaneously, the copper corrosion rate is significantly reduced to as low as 56 Å / min, and the butterfly-shaped depressions in the polished copper are also improved.

Description

Technical Field

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

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

[0003] Fabricating through-silicon vias (TSVs) on the back of chips using complex processes is crucial for achieving three-dimensional stacking between chips. The process mainly involves the following steps: 1. Efficient etching to form numerous vias; 2. Filling the vias with dielectric, adhesion, barrier, and metal layers; 3. Removing the covering metal layer using chemical mechanical polishing (CMP) to achieve planarization and circuit continuity. Due to the significant depth of TSVs, the copper plating thickness in TSV processes is much greater than that of copper interconnects in integrated circuits, reaching 2-10 μm, or even tens of micrometers. Therefore, higher requirements are placed on the polishing process of the copper film layer in TSVs: achieving a high copper removal rate under lower pressure to improve production efficiency, while avoiding localized and overall corrosion, reducing the butterfly-shaped depressions in the polished copper, and providing a suitable process for subsequent barrier layer polishing.

[0004] However, with the continuous maturation of 3D packaging technology and the increasing application of through-silicon via (TSV) technology, existing copper polishing slurries, while improving the copper film removal rate, have failed to address issues such as localized or overall excessive corrosion of the copper in high-speed copper polishing applications. Furthermore, existing technologies widely use azoles as corrosion inhibitors; however, azoles readily bind to the copper film to form a relatively dense molecular film, affecting the polishing rate and hindering subsequent cleaning processes, resulting in organic residues on the surface.

[0005] Therefore, developing a high-speed chemical mechanical polishing slurry that can improve the overall copper layer removal rate without causing localized or overall corrosion is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

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

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

[0008] The corrosion inhibitor has the structure of Formula 1;

[0009] ;

[0010] 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.

[0011] In some specific implementations, the abrasive particles include one or more of the following: SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3 and their co-formed products, soft abrasives based on organic polymers, or particles modified with silane coupling agents.

[0012] And / or, the particle size of the abrasive particles is 20~200nm;

[0013] 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;

[0014] And / or, the chelating agent includes one or more amino acids and amino acid derivatives;

[0015] And / or, in the structure of Formula 1 of the corrosion inhibitor, R1 is a straight-chain alkyl group from C9 to C17, and R2 and R3 are each independently -H, -CH3 or -CH2CH3;

[0016] And / or, the pH of the corrosion-resistant through-silicon via copper film chemical mechanical polishing solution is 5-9.

[0017] In some specific implementations, the abrasive particles include one or more of SiO2, Al2O3, or CeO2;

[0018] And / or, the particle size of the grinding particles is 30~150nm;

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

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

[0021] And / or, the corrosion inhibitor comprises 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;

[0022] And / or, the pH of the corrosion-resistant through-silicon via copper film chemical mechanical polishing solution is 6-8.

[0023] In some specific implementations, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry includes SiO2 abrasive particles, glycine, lauramide propyl dimethylamine, H2O2, and water;

[0024] Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry comprises SiO2 abrasive particles, glycine, N-(3-aminopropyl)octamide, H2O2, and water;

[0025] Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry comprises SiO2 abrasive particles, glycine, N-[2-(2-hydroxyethylamino)ethyl]dodecanoamide, H2O2, and water;

[0026] Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry comprises SiO2 abrasive particles, glycine, N-(3-aminopropyl)dodecanoamide, H2O2, and water;

[0027] Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry comprises SiO2 abrasive particles, glycine, N-octadecanoyl ethylenediamine, H2O2, and water;

[0028] Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry comprises SiO2 abrasive particles, sarcosine, lauramide propyl dimethylamine, H2O2, and water;

[0029] Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry includes SiO2 abrasive particles, DL-alanine, lauramide propyl dimethylamine, H2O2, and water;

[0030] Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry includes SiO2 abrasive particles, glycine, lauramide propyl dimethylamine, potassium bromate, and water.

[0031] In some specific implementations, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry also includes one or more of the following: pH adjuster, surfactant, and bactericide.

[0032] In some specific implementations, the pH adjuster is an acid adjuster, which is selected from organic acids or inorganic acids. The inorganic acid is selected from one or more of hydrochloric acid, phosphoric acid, nitric acid, or sulfuric acid, and the organic acid is selected from one or more of succinic acid, malonic acid, tartaric acid, or gluconic acid.

[0033] And / or, the pH adjuster is an alkaline adjuster, the alkaline adjuster is selected from inorganic bases or organic bases, the inorganic base is selected from one or more of ammonium hydroxide, potassium hydroxide or sodium hydroxide, and the organic base is selected from one or more of tetraalkylammonium hydroxide, ethanolamine, ethylenediamine or diethylamine;

[0034] And / or, the surfactant is selected from one or more of alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfates, alkyl phosphates, sodium lauryl 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, straight-chain secondary alcohol polyoxyethylene ether, polyethylene glycol stearate, acetylation diol ethoxylated compound, alkyl ammonium salt or alkylpyridinium salt;

[0035] And / or, the bactericide is selected from one or both of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.

[0036] In some specific implementations, the abrasive particles in the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry contain 0.002% to 20% by mass.

[0037] And / or, the oxidant has a mass percentage of 0.1-10% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry;

[0038] And / or, the chelating agent has a mass percentage of 0.1% to 15% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing solution;

[0039] And / or, the corrosion inhibitor has a mass percentage content of 0.005~1% in the corrosion-resistant silicon through-hole copper film chemical mechanical polishing slurry.

[0040] In some specific implementations, the abrasive particles in the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry contain 0.02% to 2% by mass.

[0041] And / or, the oxidant has a mass percentage of 0.5-5% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry;

[0042] And / or, the chelating agent has a mass percentage of 0.5-10% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing solution;

[0043] And / or, the corrosion inhibitor has a mass percentage content of 0.01~0.5% in the corrosion-resistant silicon through-hole copper film chemical mechanical polishing slurry.

[0044] This application also provides an application of the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry as described above, for use on the surface of a semiconductor substrate with copper plating, copper wiring, or through-silicon via copper, comprising: contacting the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry with the semiconductor substrate to be polished and performing chemical mechanical polishing treatment; wherein the surface of the semiconductor substrate to be polished comprises at least one copper or at least a portion of a copper-containing surface.

[0045] In some specific implementations, the semiconductor substrate to be polished further includes a barrier layer and / or a dielectric layer, wherein the barrier layer includes one or more of Ta, TaN, Ti, TiN or SiN; and the dielectric layer includes one or more of TEOS, low k or ultra-low k.

[0046] The corrosion-resistant chemical mechanical polishing (CMP) slurry for polishing copper films in through-silicon vias (TSVs) provided in this application achieves a high and adjustable copper film removal rate under relatively low downpressure conditions, significantly improving production efficiency while effectively inhibiting local and overall corrosion of the metal material, thereby improving product yield. Furthermore, it maintains a low butterfly-shaped depression during high-speed copper film removal, laying a good foundation for subsequent barrier layer polishing. In addition, this CMP composition exhibits excellent polishing selectivity, enabling highly selective removal of the copper film relative to barrier layers (such as Ta, TaN, Ti, TiN, or SiN) and dielectric layers (such as TEOS, low-k, or ultra-low-k). This polishing slurry is free of azole corrosion inhibitors, avoiding negative impacts on the copper removal rate, and is easy to clean.

[0047] Applying corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry to TSV copper film polishing can achieve a copper removal rate of up to 36971 Å / min under a low pressure of 2 psi, and the copper removal rate is adjustable (15321~36971 Å / min). At the same time, the copper corrosion rate is significantly reduced to as low as 31 Å / min, and the butterfly-shaped depressions of the copper after polishing are also improved. Detailed Implementation

[0048] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.

[0049] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.

[0050] It should be understood that the order of steps or the sequence of actions is not important as long as this application remains operational. Furthermore, two or more steps or actions can be performed simultaneously.

[0051] The use of any and all instances or exemplary language such as “e.g.” or “include” in this document is intended merely to better illustrate the application and does not constitute a limitation on the scope of the application. No language in this specification should be construed as indicating that any unclaimed element is essential to the practice of this application.

[0052] Furthermore, the numerical ranges and parameters used to define this application are approximate values, and the relevant values ​​in the specific embodiments have been presented as precisely as possible. However, any numerical value inevitably contains standard deviations due to individual test methods. Therefore, unless otherwise explicitly stated, it should be understood that all ranges, quantities, values, and percentages used in this disclosure are modified with the word "approximately." Here, "approximately" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a specific value or range.

[0053] This application provides a corrosion-resistant chemical mechanical polishing slurry for through-silicon via copper films, comprising: abrasive particles, an oxidant, a chelating agent, a corrosion inhibitor, and water;

[0054] The corrosion inhibitor has the structure of Formula 1;

[0055] ;

[0056] Wherein, R1 is a straight-chain alkyl group from C7 to C17 (which can be C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17), R2 and R3 are each independently -H, -CH3, -CH2CH3 or -CH2CH2OH, and m is 2 or 3.

[0057] The corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry described in this application includes a corrosion inhibitor. In some specific implementations, R1 is a C9 to C17 straight-chain alkyl group, and R2 and R3 are each independently -H, -CH3, or -CH2CH3. In some specific implementations, the corrosion inhibitor includes, but is not limited to, one or more of N-(3-aminopropyl)dodecanoamide, N-(3-aminopropyl)octanoamide, octanoamide-propyl dimethyl tertiary amine, decanamide-propyl dimethyl tertiary amine, N-[2-(2-hydroxyethylamino)ethyl]dodecanoamide, palmitamide-propyl diethylamine, myristamide-propyl dimethylamine, N-[2-(diethylamino)ethyl]stearamide, stearamide-propyl dimethylamine, stearamide-ethyl diethylamine, N-octadecanoyl ethylenediamine, or lauramide-propyl dimethylamine. The corrosion inhibitor is an N-acyldiamine compound, with an amide group at one end bearing a long-chain alkyl group and an amino group or a substituted amino group at the other end, the two being interconnected by an ethylidene or propyleneide group. The corrosion inhibitor has a mass percentage content of 0.005% to 1%, and can be 0.005%, 0.01%, 0.02%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.8%, 0.9%, 0.95%, or 1%. In some specific implementations, the corrosion inhibitor has a mass percentage content of 0.01% to 0.5% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry.

[0058] This application requires that corrosion inhibitors must have long-chain alkyl groups in order to improve the effect of local and overall corrosion. The long-chain alkyl group refers to a group with more than 7 carbon atoms and no more than 17 carbon atoms, because an excessively long chain will result in too many carbon atoms and cause the corrosion resistance to deteriorate.

[0059] Traditional copper polishing slurries typically use azoles as corrosion inhibitors. However, azoles readily bind to the copper film, forming a dense molecular film that significantly reduces the removal rate of the copper film and hinders subsequent cleaning processes. This application's corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry selects a novel corrosion inhibitor that effectively reduces both localized and overall copper corrosion. The copper surface maintains its original metallic luster. Furthermore, during polishing, under shear force, the inhibitor continuously detaches from and re-bonds to the copper surface in a dynamic manner, thus maintaining a high copper removal rate.

[0060] Furthermore, the corrosion inhibitor selected in the corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry provided in this application can also protect the copper film layer from excessive removal during the over-polishing time by adsorbing onto the surface of the copper film layer within the trench, thus improving the butterfly-shaped depressions after polishing. Because it also adsorbs onto the copper layer surface at higher steps, the overall copper film removal rate decreases slightly. Specifically, the polishing slurry provided in this application can achieve a copper removal rate of over 35,000 Å / min under a low pressure of 2 psi, and is generally weakly alkaline to neutral, effectively reducing the corrosion of the polishing slurry on the equipment.

[0061] The corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry described in this application includes abrasive particles. In some specific implementations, the abrasive particles include, but are not limited to, one or more of the following: SiO2, Al2O3, CeO2, TiO2, ZrO2, Fe2O3 co-formed products, soft abrasive particles based on organic polymers, or particles surface-modified with silane coupling agents. The soft abrasive particles based on organic polymers include one or more of the following: polyethylene, polytetrafluoroethylene, polyurethane, polyacrylic acid, polymethacrylic acid, polyacrylate, polymethyl methacrylate, polypropylene, polybutadiene, and common polymer abrasives commonly used for chemical mechanical polishing. This application does not have special requirements for the selection of abrasive particles. In some specific implementations, the abrasive particles include one or more of SiO2, Al2O3, or CeO2; the particle size of the abrasive particles is 30~150nm, such as abrasive particles with alumina doped on or inside the surface of silicon oxide, which can achieve the corresponding effect. The abrasive particles may have a narrow or wide particle size distribution, and may have various sizes and shapes. The shapes of the abrasive particles include spherical, cocoon-shaped, string-shaped, curved, and various other shapes. This application does not have specific requirements for the shape of the abrasive particles. In some specific implementations, the particle size of the abrasive particles is 20~200nm, and can be 20nm, 30nm, 50nm, 60nm, 70nm, 80nm, 100nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, or 200nm, preferably 30~150nm. The mass percentage of the grinding particles is from 0.002% to 20%, and can be 0.002%, 0.005%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.1%, 0.5%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 5%, 10%, 15%, 18%, 20%, preferably from 0.02% to 2%.

[0062] The corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry described in this application includes an oxidizing agent. In some specific implementations, the oxidizing agent includes one or more of the following: inorganic peroxides, persulfides, organic peroxides, hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate, hypobromic acid, hypobromite, bromic acid, bromate, perbromic acid, perbromite, hypoiodic acid, hypoiodate, iodic acid, iodate, periodic acid, periodate, chromic acid, chromate, iron salts, copper salts, ferricyanide, or molybdates. This application does not have specific requirements for the selection of the oxidizing agent. In some specific implementations, the oxidizing agent includes one or more of the following: hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, or 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%. In some specific implementations, the oxidant has a mass percentage content of 0.5% to 5% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry.

[0063] The corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry described in this application includes a chelating agent. In some specific implementations, the chelating agent includes one or more amino acids and amino acid derivatives. In some specific implementations, the chelating agent includes one or more of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, or iminodiacetic acid. This application does not have special requirements for the selection of the chelating agent, but glycine is preferred. The mass percentage of the chelating agent is 0.1% to 15%, and can be 0.1%, 0.2%, 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.5%, 10%, or 15%, preferably 0.5% to 10%. In some specific implementations, the chelating agent has a mass percentage of 0.5-10% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry.

[0064] In some specific implementations, the corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing (CMP) slurry comprises SiO2 abrasive particles, glycine, lauramide propyl dimethylamine, H2O2, and water. In some specific implementations, the corrosion-resistant TSV copper film CMP slurry comprises SiO2 abrasive particles, glycine, N-(3-aminopropyl)octylamide, H2O2, and water. In some specific implementations, the corrosion-resistant TSV copper film CMP slurry comprises SiO2 abrasive particles, glycine, N-[2-(2-hydroxyethylamino)ethyl]dodecanoamide, H2O2, and water. In some specific implementations, the corrosion-resistant TSV copper film CMP slurry comprises SiO2 abrasive particles, glycine, N-(3-aminopropyl)dodecanoamide, H2O2, and water. In some specific implementations, the corrosion-resistant TSV copper film CMP slurry comprises SiO2 abrasive particles, glycine, N-octadecanoyl ethylenediamine, H2O2, and water. In some specific implementations, the corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing (CMP) slurry comprises SiO2 abrasive particles, sarcosine, lauramidopropyl dimethylamine, H2O2, and water. In some specific implementations, the corrosion-resistant TSV copper film CMP slurry comprises SiO2 abrasive particles, DL-alanine, lauramidopropyl dimethylamine, H2O2, and water. In some specific implementations, the corrosion-resistant TSV copper film CMP slurry comprises SiO2 abrasive particles, glycine, lauramidopropyl dimethylamine, potassium bromate, and water.

[0065] In some specific implementations, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry also includes one or more of the following: pH adjuster, surfactant, and bactericide.

[0066] The corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry described in this application includes a pH adjuster. In some specific implementations, the pH adjuster is an acid adjuster, selected from organic or inorganic acids. The inorganic acid is selected from one or more of hydrochloric acid, phosphoric acid, nitric acid, or sulfuric acid, and the organic acid is selected from one or more of succinic acid, malonic acid, tartaric acid, or gluconic acid. In some specific implementations, the pH adjuster is an alkali adjuster, selected from inorganic or organic alkalis. The inorganic alkali is selected from one or more of ammonium hydroxide, potassium hydroxide, or sodium hydroxide, and the organic alkali is selected from one or more of tetraalkylammonium hydroxide, ethanolamine, ethylenediamine, or diethylamine. The pH adjuster is used to adjust the corrosion-resistant TSV copper film chemical mechanical polishing slurry, resulting in a pH value of 5 to 9, specifically 5, 6, 7, 7.3, 8, or 9. In some specific implementations, the pH of the corrosion-resistant TSV copper film chemical mechanical polishing slurry is 6 to 8.

[0067] The corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry described in this application includes a bactericide. In some specific implementations, the bactericide is selected from one or both of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.

[0068] The corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry described in this application includes a surfactant. In some specific implementations, the surfactant is selected from one or more of the following: alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfates, alkyl phosphates, sodium fatty alcohol polyoxyethylene ether sulfate, sarcosinates, taurines, polyacrylic acid, polyethers, polyoxyethylene ether phosphates, polyethylene glycol, polyvinyl alcohol, polyvinyl butyral, cellulose, polyethyleneimine, polyvinylpyrrolidone, ethoxypropoxylated fatty alcohols, alkoxylated branched fatty alcohols, linear secondary alcohol polyoxyethylene ethers, polyethylene glycol stearate, acetylacetonate ethoxylated compounds, alkylammonium salts, or alkylpyridinium salts.

[0069] This application also provides an application of the corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry as described above, for use on the surface of a semiconductor substrate with copper plating, copper wiring, or through-silicon via (TSV) copper, comprising: contacting the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry with the semiconductor substrate to be polished and performing chemical mechanical polishing treatment; wherein the surface of the semiconductor substrate to be polished comprises at least one copper or at least a portion of a copper-containing surface.

[0070] In some specific implementations, the semiconductor substrate to be polished further includes a barrier layer and / or a dielectric layer, wherein the barrier layer includes one or more of Ta, TaN, Ti, TiN or SiN; and the dielectric layer includes one or more of TEOS, low k or ultra-low k.

[0071] The present application is further illustrated below with reference to embodiments. The scope of protection of the present application is not limited to the following embodiments.

[0072] The specific components of the corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry in the embodiments and comparative examples of this application are calculated based on the content of pure substances and prepared according to the formulas given in Tables 1-4, with the balance being water (the percentages in the tables all represent mass percentages). All components are mixed evenly, and the pH is adjusted to the required value using nitric acid or potassium hydroxide before further mixing to obtain the corrosion-resistant TSV copper film chemical mechanical polishing slurry. The content of each component in the corrosion-resistant TSV copper film chemical mechanical polishing slurry represents the actual concentration used during the polishing process; commercially available products can be appropriately concentrated.

[0073] Table 1

[0074]

[0075] Table 2

[0076]

[0077] Table 3

[0078]

[0079] Table 4

[0080]

[0081] The performance of the corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurries provided in Examples 1-15 and the through-silicon via (TSV) copper film polishing slurries provided in Comparative Examples 1-9 was tested using the following methods:

[0082] The polishing slurries prepared in the examples and comparative examples were used to polish the samples to be polished. The samples to be polished were 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. The 854 structure wafers were polished until no copper film residue remained. The polishing machine used was SIZONE TENMS-200 Plus, the polishing pad was IC1010, and the polishing head and polishing disk speeds were 93 rpm and 87 rpm, or 108 rpm and 102 rpm, respectively. The polishing slurry flow rate was 150 mL / min.

[0083] The metal film thickness measuring instrument is a NAPSON RG3000, which uses 49 points to measure the change in film thickness before and after polishing, thereby calculating the polishing rate. The dielectric film thickness measuring instrument is a FILMETRICS F54-XYT-300, which also uses 49 points to measure the change in film thickness before and after polishing, thereby calculating the polishing rate.

[0084] The butterfly-shaped indentation measuring machine is a KLA-Tencor P-17, which measures two feature patterns: 50um×50um and 10um×10um. The height difference between the two platforms relative to the middle indentation is the indentation value.

[0085] Comparative Examples 1-7 were selected to polish Cu substrates under the same process conditions, and the polishing results with removal rates are listed in Table 5.

[0086] Table 5

[0087]

[0088] As shown in Table 5, adding amino acids or amino acid derivatives as copper ion chelating agents can significantly improve the removal rate of copper oxides by the abrasive particles. The polishing results of Comparative Examples 1-5 show that when glycine is used as a chelating agent, this polishing system can achieve a high copper film removal rate at a low pressure of 2 psi. The results of Comparative Examples 7-8 indicate that the copper film removal rate can be adjusted by changing the content of the abrasive particles; considering the balance between performance and cost, a silica sol content of 0.5% is a suitable value.

[0089] Comparative Examples 5, 8-9 and Examples 1-8 of this application were selected to perform polishing and static etching tests on Cu substrates under the same conditions. The results of removal rate and etching rate are listed in Table 6.

[0090] Table 6

[0091]

[0092] As shown in Table 6, Comparative Example 5 and Examples 1-6 demonstrate that in the Cu polishing composition using glycine as a chelating agent, the corrosion inhibitor described in this application effectively improved the corrosion phenomenon on the copper film surface. When the amount of lauramidopropyl dimethylamine added was 0.1%, the corrosion rate of the Cu film at room temperature decreased to 56 Å / min, while a high Cu film removal rate was still maintained at a pressure of 2 psi. In contrast, the results of Comparative Examples 8-9 show that when 1,2,4-triazole was used as a corrosion inhibitor, it easily combined with the copper film to form a relatively dense molecular film. Although the corrosion phenomenon on the Cu surface was controlled at an addition amount of 0.20%, it significantly affected the removal rate of the Cu film at low pressures. When N-(3-aminopropyl)acetamide with a shorter carbon chain was selected as a corrosion inhibitor, the results of Comparative Example 10 showed that the corrosion phenomenon on the Cu film surface could not be effectively controlled. The results of Examples 7-8 indicate that the corrosion inhibitor described in this application is also applicable to other amino acid systems.

[0093] Comparative Example 5, Example 2, and Examples 9-10 of this application were selected to polish Cu substrates and Cu structural sheets under the same conditions. The results of the removal rate and butterfly indentation value are listed in Table 7.

[0094] Table 7

[0095]

[0096] Based on the data in Table 7, the polishing results of Comparative Example 5 and Example 2 show that adding lauramidopropyl dimethylamine, a corrosion inhibitor, to the corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry containing glycine as a chelating agent reduces the surface corrosion rate of the copper film and significantly improves the butterfly-shaped depressions after polishing. With an addition of 0.1% lauramidopropyl dimethylamine, the depression value of 50 μm × 50 μm decreased by 39.8%, and the depression value of 10 μm × 10 μm decreased by 35.6%. Comparing the polishing results of Examples 2, 9, and 10, it is clear that reducing the particle size is beneficial for improving the butterfly-shaped depression value after polishing. Reducing the silicon oxide particle size from 98 nm to 27 nm resulted in a 26.2% decrease in the depression value of 50 μm × 50 μm and a 17.4% decrease in the depression value of 10 μm × 10 μm, while the polishing rate also decreased by 11.3%.

[0097] Examples 2 and 11-15 of this application were selected to polish Cu substrates under the same conditions, and the results of the removal rate are listed in Table 8.

[0098] Table 8

[0099]

[0100] Comparing the polishing results of Examples 2 and 11-12, it can be seen that the Cu polishing composition of this application achieves the highest Cu film removal rate at pH=7.3 and a pressure of 2 psi, and the lowest Cu film removal rate at pH=8.5, but both are still high. As shown in Examples 13-15, the removal rate of the polishing composition on the Cu substrate can be adjusted by increasing or decreasing the hydrogen peroxide content. At a hydrogen peroxide addition of 2%, the composition achieves the highest Cu film removal rate at a pressure of 2 psi. Under the tested pH and hydrogen peroxide content conditions, the Cu polishing composition of this application can provide a high Cu removal rate at a relatively low pressure.

[0101] Example 2 was used to measure the selectivity of the Cu film relative to other barrier layers such as Ta, TaN, Ti, and TiN, as well as dielectric films such as TEOS. Table 9 lists the selectivity results when a downpressure of 2 psi is used.

[0102] Table 9

[0103]

[0104] As shown in Table 9, during chemical mechanical polishing, the removal rate of Cu film by the corrosion-resistant through-silicon via (TSV) copper film chemical mechanical polishing slurry is much higher than that of other substrate materials. This high selectivity of polishing is highly desirable for many applications that require high copper film removal rates, such as TSV applications.

[0105] Based on the above test results, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry of this application can remove the copper film layer at a relatively fast speed, and can effectively improve the local and overall corrosion of metal materials, and reduce the butterfly-shaped depressions of copper after polishing. It is worth mentioning that the concentrations of each component in the above embodiments are the actual amounts used in the polishing process. This system can be appropriately concentrated and kept in a stable state, so as to facilitate production, transportation and use at the client end.

[0106] The above description is merely a preferred embodiment of this application, but the scope of protection of this application is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in this application, based on the technical solution and application concept of this application, should be included within the scope of protection of this application.

Claims

1. A corrosion-resistant chemical mechanical polishing slurry for through-silicon via copper films, characterized in that, include: Abrasive particles, oxidant, chelating agent, corrosion inhibitor, and water; The corrosion inhibitor has the structure of Formula 1; ； Wherein, R1 is a straight-chain alkyl group from C7 to C17, R2 and R3 are each independently -H, -CH3, -CH2CH3 or -CH2CH2OH, and m is 2 or 3; The grinding particles include SiO2; Oxidizing agents include one or more of hydrogen peroxide, potassium bromate, potassium iodate, ferric nitrate, sodium hypochlorite, or sodium perchlorate; The chelating agent includes one or more of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, or iminodiacetic acid. The particle size of the grinding particles is 20~200nm; The pH of the corrosion-resistant through-hole copper film chemical mechanical polishing solution is 5-9; The abrasive particles constitute 0.002% to 20% of the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry by mass percentage. The oxidant has a mass percentage of 0.1% to 10% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry; The chelating agent has a mass percentage of 0.1% to 15% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry; The corrosion inhibitor has a mass percentage content of 0.005~1% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry.

2. The corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry according to claim 1, characterized in that, In the structure of Formula 1 of the corrosion inhibitor, R1 is a straight-chain alkyl group from C9 to C17, and R2 and R3 are each independently -H, -CH3 or -CH2CH3.

3. The corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry according to claim 1, characterized in that, The particle size of the grinding particles is 30~150nm; And / or, the corrosion inhibitor comprises 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; And / or, the pH of the corrosion-resistant through-silicon via copper film chemical mechanical polishing solution is 6-8.

4. The corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry according to claim 1, characterized in that, The corrosion-resistant through-hole copper film chemical mechanical polishing slurry includes SiO2 abrasive particles, glycine, lauramide propyl dimethylamine, H2O2, and water; Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry comprises SiO2 abrasive particles, glycine, N-(3-aminopropyl)octamide, H2O2, and water; Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry comprises SiO2 abrasive particles, glycine, N-[2-(2-hydroxyethylamino)ethyl]dodecanoamide, H2O2, and water; Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry comprises SiO2 abrasive particles, glycine, N-(3-aminopropyl)dodecanoamide, H2O2, and water; Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry comprises SiO2 abrasive particles, glycine, N-octadecanoyl ethylenediamine, H2O2, and water; Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry comprises SiO2 abrasive particles, sarcosine, lauramide propyl dimethylamine, H2O2, and water; Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry includes SiO2 abrasive particles, DL-alanine, lauramide propyl dimethylamine, H2O2, and water; Alternatively, the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry includes SiO2 abrasive particles, glycine, lauramide propyl dimethylamine, potassium bromate, and water.

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

6. The corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry according to claim 5, characterized in that, The pH adjuster is an acid adjuster, which is selected from organic acids or inorganic acids. The inorganic acid is selected from one or more of hydrochloric acid, phosphoric acid, nitric acid or sulfuric acid, and the organic acid is selected from one or more of succinic acid, malonic acid, tartaric acid or gluconic acid. And / or, the pH adjuster is an alkaline adjuster, the alkaline adjuster is selected from inorganic bases or organic bases, the inorganic base is selected from one or more of ammonium hydroxide, potassium hydroxide or sodium hydroxide, and the organic base is selected from one or more of tetraalkylammonium hydroxide, ethanolamine, ethylenediamine or diethylamine; And / or, the surfactant is selected from one or more of alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfates, alkyl phosphates, sodium lauryl 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, straight-chain secondary alcohol polyoxyethylene ether, polyethylene glycol stearate, acetylation diol ethoxylated compound, alkyl ammonium salt or alkylpyridinium salt; And / or, the bactericide is selected from one or both of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.

7. The corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry according to claim 1, characterized in that, The abrasive particles constitute 0.02% to 2% of the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry by mass percentage. And / or, the oxidant has a mass percentage of 0.5-5% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing slurry; And / or, the chelating agent has a mass percentage of 0.5-10% in the corrosion-resistant through-silicon via copper film chemical mechanical polishing solution; And / or, the corrosion inhibitor has a mass percentage content of 0.01~0.5% in the corrosion-resistant silicon through-hole copper film chemical mechanical polishing slurry.

8. The application of a corrosion-resistant chemical mechanical polishing slurry for through-silicon via copper films as described in any one of claims 1 to 7, characterized in that, Semiconductor substrates for copper-plated, copper-wired, or through-silicon via (TSV) copper surfaces include: contacting a corrosion-resistant 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.

9. The application according to claim 8, 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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