Pad-in-bottle (PIB) technology for copper and through-silicon via (TSV) chemical mechanical planarization (CMP)

Abstract

Providing pad-in-bottle technology. A novel pad-in-a-bottle (PIB) technology for advanced chemical mechanical planarization (CMP) copper or through-silicon-via (TSV) CMP compositions, systems, and processes is disclosed in which the role of traditional polishing pad asperities is fulfilled by high-quality micron-sized polyurethane (PU) beads that match the size of the polishing pad pores and asperities.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the benefit of U.S. Provisional Application No. 63 / 058,289, filed Jul. 29, 2020, which is hereby incorporated by reference in its entirety as if fully set forth herein.

Background Art

[0002] Background of the Invention The present invention generally relates to novel pad - in - a - bottle (PIB) technology for advanced chemical mechanical planarization (CMP) compositions, systems, and processes. Specifically, the present invention relates to PIB technology for advanced copper and TSV CMP compositions, systems, and processes.

[0003] In CMP, the unevenness on a polyurethane (PU) pad is irreversibly deformed by wafer contact and also worn by composition particles. Therefore, to ensure process stability, the pad surface must be continuously updated with a diamond disk. Since the diamond disk has to cut the pad surface to remove old unevenness and create new ones, they also gradually thin the pad, making its replacement necessary (FIG. 1).

[0004] Thus, conventional CMP has several weaknesses such as (a) generating a large amount of waste (due to frequent replacement of pads and conditioners), and (b) the uneven shape of the pad not being controlled, resulting in large variations in the contact area distribution. These lead to variations in the removal rate (RR), which particularly affects wafer - level topography.

[0005] The present invention discloses a new and novel pad - in - a - bottle (PIB) technology for advanced node copper and TSV CMP compositions, systems, and processes developed to meet challenging requirements.

Summary of the Invention

[0006] SUMMARY OF THE INVENTION The needs are satisfied by using the disclosed compositions, methods, and planarization systems for CMP of copper and TSV substrates.

[0007] In one aspect, a CMP polishing composition is provided. The CMP polishing composition comprises an abrasive, micron-sized polyurethane (PU) beads having a size in the range of 2 to 100 μm, 10 to 80 μm, 20 to 70 μm, or 30 to 50 μm; a silicone-containing dispersant; a liquid carrier such as water; and optionally, a chelating agent, a corrosion inhibitor, an organic quaternary ammonium salt, a biocide; a pH adjuster; including an oxidizing agent added during use; the pH of the composition is 3.0 to 12.0; 4.0 to 11.0; 5.0 to 10.0; 5.5 to 9.0; 6.0 to 8.0; or 6.0 to 7.5.

[0008] In another aspect, a CMP polishing method is provided. The CMP polishing method comprises providing a semiconductor substrate having a surface containing copper or through-silicon via (TSV) copper; providing a polishing pad; providing the above-described chemical mechanical polishing (CMP) formulation; contacting the surface of the semiconductor substrate with the polishing pad and the chemical mechanical polishing formulation; and polishing the surface of the semiconductor; at least a portion of the surface containing the Cu film is in contact with both the polishing pad and the chemical mechanical polishing formulation.

[0009] In yet another aspect, a CMP polishing system is provided. The CMP polishing system comprises a semiconductor substrate having a surface containing copper or through-silicon via (TSV) copper; Providing an abrasive pad; Including providing a chemical mechanical polishing (CMP) composition of the above claims; At least a part of the surface containing the Cu film is in contact with both the abrasive pad and the chemical mechanical polishing composition.

[0010] The abrasive includes, but is not limited to, colloidal silica or high-purity colloidal silica; colloidal silica particles doped with other metal oxides within the lattice of colloidal silica such as alumina-doped silica particles; colloidal aluminum oxide such as α-, β-, and γ-aluminum oxide; colloidal and photoactive titanium dioxide, cerium oxide, colloidal cerium oxide, nano-sized inorganic metal oxide particles such as alumina, titania, zirconia, ceria, etc.; nano-sized diamond particles, nano-sized silicon nitride particles; monomodal, bimodal, multimodal, colloidal abrasive particles; flexible abrasive particles based on organic polymers, abrasive particles with coated or modified surfaces, or other composite particles, and mixtures thereof.

[0011] Examples of the silicone-containing dispersant include, but are not limited to, silicone polyethers containing both a water-insoluble silicone backbone and many water-soluble polyether pendant groups that provide surface wetting properties. An example is a silicone polyether containing a water-insoluble silicone backbone and pendant groups containing n repeating units (n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups.

[0012] Examples of corrosion inhibitors include, but are not limited to, families of heteroaromatic compounds containing one or more nitrogen atoms in the aromatic ring, such as 1,2,4-triazole, amitrole (3-amino-1,2,4-triazole), benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, and tetrazole and tetrazole derivatives.

[0013] Examples of chelating agents (or chelating agents) include, but are not limited to, amino acids and their derivatives, and organic amines.

[0014] Examples of amino acids and their derivatives include, but are not limited to, glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, and combinations thereof.

[0015] Examples of organic amines include, but are not limited to, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, etc.

[0016] Organic diamine compounds containing two primary amine moieties can be described as binary chelating agents.

[0017] Examples of biocides include, but are not limited to, Kathon (trademark) and Kathon (trademark) CG / ICP II from Dow Chemical. They have active ingredients of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.

[0018] Examples of the oxidizing agent include, but are not limited to, periodic acid, hydrogen peroxide, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and mixtures thereof.

[0019] Examples of the organic quaternary ammonium salt as a Cu removal rate accelerator and a defect reducer include, but are not limited to, choline salts having various counterions such as choline bicarbonate, choline hydroxide, choline dihydrogen citrate salt, choline ethanolamine, and choline bitartrate.

[0020] Examples of the pH adjuster include, but are not limited to, the following: nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof for adjusting the pH in the acidic direction. Examples of the pH adjuster also include basic pH adjusters such as sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkylammonium hydroxide, organic amines, and other chemical reagents that can be used to adjust the pH in the more alkaline direction. BRIEF DESCRIPTION OF THE DRAWINGS

[0021]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

[0022] Detailed Description of the Invention This disclosure presents a new technology where the role of pad asperities is fulfilled by high-quality micron-sized polyurethane (PU) beads having sizes in the range of 2 to 100 μm, 10 to 80 μm, 20 to 70 μm, or 30 to 50 μm; these sizes are comparable to the pore and asperity sizes of commercially available polishing pads.

[0023] The beads are suspended in a Cu CMP polishing composition having abrasive particles such as fired ceria, colloidal silica, or composite particles, with the aid of a wetting agent (or surfactant) as a dispersant for dispersing the polyurethane beads in the aqueous composition.

[0024] Figure 2 shows PIB CMP polishing with a polyurethane pad 146 and polyurethane beads (130). The beads contact the wafer surface by the means described below and promote polishing much like conventional asperities.

[0025] By selecting both the size of the beads and their concentration in the composition, much better control of the height, curvature, and areal density of the "apexes" contacting the wafer is achieved, and the process variations associated with conventional asperity contact are significantly reduced.

[0026] The use of beads still requires a second surface, or counter surface, where polishing occurs, which in our case continues to be a conventional polyurethane-based pad, but since it is no longer the main surface where polishing occurs, the conditioning required is minimal. Instead, as the counter surface of FIG. 2, an inexpensive, partially conditioned pad can be used.

[0027] The polisher may use two or three pads and conditioners simultaneously. Typically, this is reached after only two days of continuous use at the end of the life of the pad and conditioning disk. Thus, since each platen of a CMP tool uses hundreds of pads and conditioners per year and a wafer fabrication facility can have dozens of tools (including two or three platens for each tool), the total cost for just the pads and pad conditioners is significant.

[0028] Since removing the used pad, installing a new pad, and qualifying it can take several hours, the tool downtime and the engineering and product losses due to the consumables used to qualify the new pad are also significant. The used PU pads and discarded diamond disk conditioners are waste from the CMP process, which causes several environmental health and safety (EHS) issues.

[0029] For the polishing pad, only about two-thirds of the pad thickness is used before the pad has to be peeled off and discarded. For the conditioner, controlling the product's service life is only a few hundred out of tens of thousands of diamonds, after which the conditioner needs to be discarded. Furthermore, recycling or reuse options are not available for pads and conditioners. Our results address the above EHS issues and provide a new solution to the current standard CMP process by eliminating the use of many pads and diamond disk conditioners.

[0030] The polyurethane beads used in the disclosed polishing compositions have a size ranging from 2 to 100 μm, 10 to 80 μm, 20 to 70 μm, or 30 to 50 μm.

[0031] Several specific aspects of the invention are outlined below.

[0032] In one aspect, a CMP polishing composition is provided. Aspect 1: abrasive material, micron-sized polyurethane (PU) beads; Silicone-containing dispersants; A liquid carrier such as water; and optionally Chelating agents; Corrosion inhibitors; Organic quaternary ammonium salts; Biocides; pH regulator; Oxidizing agent added at the time of use CMP polishing composition comprising: A CMP polishing composition, wherein the pH of the composition is 3.0 to 12.0; 4.0 to 11.0; 5.0 to 10.0; 5.5 to 9.0; 6.0 to 8.0; or 6.0 to 7.5.

[0033] Aspect 2: providing a semiconductor substrate having a surface containing copper or TSV copper; Providing a polishing pad; providing a chemical mechanical polishing (CMP) formulation as described above; contacting a surface of a semiconductor substrate with a polishing pad and a chemical mechanical polishing formulation; and Polishing the surface of a semiconductor A CMP polishing method comprising: A CMP polishing method, wherein at least a portion of a surface containing a Cu film is in contact with both a polishing pad and a chemical mechanical polishing formulation.

[0034] Aspect 3: A semiconductor substrate having a surface containing a Cu film; Providing a polishing pad; Providing a chemical mechanical polishing (CMP) formulation according to the above claims. 1. A CMP polishing system comprising: A CMP polishing system, wherein at least a portion of a surface containing a Cu film is in contact with both a polishing pad and a chemical mechanical polishing formulation.

[0035] The abrasives are nano-sized abrasive particles, including, but not limited to, colloidal silica or high purity colloidal silica; colloidal silica particles doped with other metal oxides within the colloidal silica lattice, such as alumina-doped silica particles; colloidal aluminum oxide, such as α-, β-, and γ-type aluminum oxide; colloidal photoactive titanium dioxide, cerium oxide, colloidal cerium oxide, nano-sized inorganic metal oxide particles, such as alumina, titania, zirconia, ceria, etc.; nano-sized diamond particles, nano-sized silicon nitride particles; monomodal, bimodal, multimodal colloidal abrasive particles; soft abrasive particles based on organic polymers, surface coated or modified abrasive particles, or other composite particles, and mixtures thereof.

[0036] Colloidal silica can be produced from silicate salts, and high-purity colloidal silica can be produced from TEOS or TMOS. Colloidal silica or high-purity colloidal silica can have a monomodal or multimodal narrow or broad particle size distribution, various sizes, and various shapes, such as spherical, cocoon, aggregate, and other shapes.

[0037] The nano-sized particles may have a variety of shapes, such as spheres, cocoons, aggregates, and the like.

[0038] The particle size of the abrasive particles used in the Cu CMP slurry ranges from 5 nm to 500 nm, from 10 nm to 250 nm, or from 25 nm to 100 nm.

[0039] The Cu CMP polishing composition contains abrasive particles in an amount of 0.0025% to 25% by mass; 0.0025% to 2.5% by mass; 0.005% to 0.5% by mass; or 0.005% to 0.15% by mass.

[0040] The CMP polishing composition contains a silicone-containing dispersant for dispersing polyurethane beads in an aqueous solution. The silicone-containing dispersant also functions as a surface wetting agent dispersant.

[0041] Examples of the silicone-containing dispersant include, but are not limited to, silicone polyethers containing both a water-insoluble silicone backbone and a number of water-soluble polyether pendant groups that provide surface wetting properties. An example is a silicone polyether containing a water-insoluble silicone backbone and pendant groups containing n repeating units (n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups.

[0042] Examples of silicone-containing dispersants include silsurf(TM) E608, silsurf(TM) J208-6, silsurf(TM) A208, silsurf(TM) CR1115, silsurf(TM) A204, silsurf(TM) A004-UP, silsurf(TM) A0 08-UP, silsurf (trademark) B608, silsurf (trademark) C208, silsurf (trademark) C410, silsurf (trademark) D208, silsurf (trademark) D208, silsurf (trademark) D208-30, silsurf (trademark) Di-1010, silsurf (trademark) Siltech™ Di-1510, silsurf™ Di-15-I, silsurf™ Di-2012, silsurf™ Di-5018-F, silsurf™ G8-I, silsurf™ J1015-O, silsurf™ J1015-O-AC, silsurf™ J208, silsurf™ J208-6, Siltech™-OP-8, Siltech™-OP-11, Siltech™-OP-12, Siltech™-OP-15, Siltech™-OP-20; products from Siltech Inc.; 225 Wicksteed Avenue, Toronto Ontario, Canada M4H 1G5.

[0043] The concentration range of the silicone-containing dispersant is 0.01% by mass to 2.0% by mass, 0.025% by mass to 1.0% by mass, or 0.05% by mass to 0.5% by mass.

[0044] The CMP slurry contains polyurethane beads of various sizes.

[0045] The polyurethane beads used in the disclosed polishing compositions have a size ranging from 2 to 100 μm, 10 to 80 μm, 20 to 70 μm, or 30 to 50 μm.

[0046] The concentration range of the polyurethane beads is 0.01% by mass to 2.0% by mass, 0.025% by mass to 1.0% by mass, or 0.05% by mass to 0.5% by mass.

[0047] Polyurethane beads are different from the disclosed abrasive particles and are not considered abrasive particles in the present disclosure.

[0048] Examples of the organic quaternary ammonium salt as a Cu removal rate accelerator and a defect reducing agent include, but are not limited to, choline salts such as choline bicarbonate, or all other salts formed between choline and other anionic counterions.

[0049] In one embodiment, the CMP slurry contains a quaternary ammonium salt in an amount of 0.005 wt% to 0.25 wt%, 0.001 wt% to 0.05 wt%; or 0.002 wt% to 0.01 wt%.

[0050] In another embodiment, the CMP slurry contains a quaternary ammonium salt in an amount of 0.005 wt% to 0.5 wt%, 0.001 wt% to 0.25 wt%; or 0.002 wt% to 0.1 wt%.

[0051] Examples of the chelating agent (or chelating agent) include, but are not limited to, amino acids, their derivatives, and organic amines.

[0052] Examples of the amino acids and their derivatives include, but are not limited to, glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, and combinations thereof.

[0053] Examples of the organic amines include, but are not limited to, 2,2-dimethyl-1,3-propanediamine, 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and the like.

[0054] An organic diamine compound containing two primary amine moieties can be described as a binary chelating agent.

[0055] The CMP slurry contains 0.1% to 18% by mass; 0.5% to 15% by mass; 1.0% to 10.0% by mass; or 2.0% to 10.0% by mass of the chelating agent.

[0056] The corrosion inhibitor can be any known and reported corrosion inhibitor.

[0057] Examples of the corrosion inhibitor include, but are not limited to, a family of heteroaromatic compounds containing one or more nitrogen atoms in the aromatic ring, such as 1,2,4-triazole, amitrole (3-amino-1,2,4-triazole), benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, and tetrazole and tetrazole derivatives.

[0058] The CMP slurry contains 0.005% to 1.0% by mass; 0.01% to 0.5% by mass; or 0.025% to 0.25% by mass of the corrosion inhibitor.

[0059] A biocide having an active ingredient for providing a more stable storage life of the Cu chemical mechanical polishing composition can be used.

[0060] Examples of the biocide include, but are not limited to, Kathon (trademark), Kathon (trademark) CG / ICP II from Dow Chemical. They have active ingredients of 5-chloro-2-methyl-4-isothiazolin-3-one and / or 2-methyl-4-isothiazolin-3-one.

[0061] The CMP slurry contains a biocide in an amount of 0.0001% to 0.05% by mass; 0.0001% to 0.025% by mass; or 0.0001% to 0.01% by mass.

[0062] The pH of the CMP polishing composition can be adjusted to an optimized pH value using an acidic or basic compound, or a pH adjuster.

[0063] Examples of pH adjusters include, but are not limited to, the following: nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof, which adjust the pH in the acidic direction. Examples of pH adjusters also include basic pH adjusters such as sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkylammonium hydroxide, organic amines, and other chemical reagents that can be used to adjust the pH in a more alkaline direction.

[0064] The CMP slurry contains a pH adjuster in an amount of 0% to 1% by mass; 0.01% to 0.5% by mass; or 0.1% to 0.25% by mass.

[0065] The pH of the Cu polishing composition is from about 3.0 to about 12.0; from about 4.0 to about 11.0; from about 5.0 to about 10.0; from about 5.5 to about 9.0, from about 6.0 to about 8.0; or from about 6.0 to about 7.5.

[0066] Using various inorganic or organic peroxide oxidants, or other types of oxidants, the metallic copper film can be oxidized to a mixture of copper oxides, enabling a rapid reaction with a chelating agent and a corrosion inhibitor.

[0067] Examples of oxidants include, but are not limited to, periodic acid, hydrogen peroxide, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and mixtures thereof. A preferred oxidant is hydrogen peroxide.

[0068] The CMP composition contains an oxidizing agent in an amount of 0.1% to 10% by mass; 0.25% to 3% by mass; or 0.5% to 2.0% by mass.

Example

[0069] Experimental section Parameters: Å: Unit of length, angstrom BP: Back pressure, in psi CMP: Chemical mechanical planarization = Chemical mechanical polishing CS: Carrier speed DF: Downward force: Pressure applied during CMP, in psi min: Minute ml: Milliliter mV: Millivolt psi: Pounds per square inch PS: Rotation speed of the polishing tool's platen, in rpm (revolutions per minute) SF: Flow rate of the polishing composition, in ml / min Removal rate (RR): Cu RR: Copper removal rate measured at a downward pressure of 1.5 psi for a 1.5 psi Cu RR 1.5 psi CMP tool Cu RR: Copper removal rate measured at a downward pressure of 2.0 psi for a 2.0 psi Cu RR 2.0 psi CMP tool Cu RR: Copper removal rate measured at a downward pressure of 3.0 psi for a 3.0 psi Cu RR 3.0 psi CMP tool

[0070] General experimental procedure Unless otherwise specified, all ratios in the composition are by mass.

[0071] In the examples shown below, the CMP experiments were carried out using the procedures and experimental conditions given below. The CMP tool used in the examples was a 200mm Mirra (trademark) polisher manufactured by Applied Materials, 3050 Boweres Avenue, Santa Clara, California, 95054. IC1000 pads or other types of polishing pads supplied by DuPont were used on the platen for blanket wafer polishing research. The pads were conditioned by polishing 25 dummy oxide (TEOS precursor, deposited by plasma enhanced CVD from PETEOS) wafers. To qualify the tool settings and pad conditioning, two PETEOS monitors were polished under baseline conditions with Syton (trademark) OX-K colloidal silica supplied by Versum Materials' planarization platform. The polishing experiments were carried out using blanket Cu wafers and Cu MIT854 200mm patterned wafers. These blanket wafers were purchased from Silicon Valley Microelectronics, 1150 Campbell Ave, CA, 95126.

[0072] A polishing pad, IC1000 pad or other polishing pad supplied by DuPont was used during Cu CMP.

[0073] Example The reference (reference) CMP composition was composed of 3.78 wt% glycine, 0.1892 wt% amitrole, 0.004 wt% ethylenediamine, 0.00963 wt% choline bicarbonate, 0.0001 wt% Kathon II biocide, and 0.0376 wt% high purity colloidal silica particles abrasive.

[0074] Silsurf E608 containing EO-PO wetting functional groups was used as the silicone-containing dispersant.

[0075] The second CMP composition (Reference 1) was prepared by adding 0.05% by mass of Silsurf E608 to the reference Cu CMP composition (Reference). The second CMP composition was used to examine the effect of the dispersant on the CMP polishing performance with respect to the reference CMP composition.

[0076] The third CMP composition (Comparison 1), the PIB-acting CMP composition, was prepared by adding 0.05% by mass of Silsurf E608 and 0.10% by mass of 35-mm-sized polyurethane beads (PU beads) to the reference Cu CMP composition (Reference).

[0077] 2.0% by mass of H2O2 was added to the CMP composition when used.

[0078] All three compositions had a pH of approximately 7.15.

[0079] The Cu removal rate was tested using those three Cu CMP compositions, and the results are shown in Table 1 and depicted in Figure 3.

Table 1

[0080] As the results shown in Table 1 and Figure 3, the Cu removal rate was reduced for the second and third CMP compositions compared to the reference Cu composition (Reference). This is due to the passivation effect of the dispersant on the copper oxide surface in the CMP polishing process.

[0081] The results also showed that the Cu removal rate by the PIB-acting CMP composition (Comparison 1) increased by about 11% compared to the Cu removal rate obtained from the second CMP composition (Reference 1).

[0082] The results showed that it is possible to increase the Cu removal rate, which is one of the advantages of using micron-sized PU beads in the Cu CMP composition.

[0083] The Cu-patterned wafers were polished using the same three CMP compositions.

[0084] In the polishing of the Cu-patterned wafers, a downward force of 1.5 psi was applied at two different slide speeds, 0.6 m / s or 1.0 m / s, respectively.

Table 2

[0085] The results of Cu line dishing obtained from the composition at a DF of 1.5 psi and a slide speed of 0.6 m / s are shown in Table 2 and plotted in Figure 4.

[0086] For the composition with the addition of only 0.05 wt% dispersant (Reference 1), Cu dishing was reduced for the 100x100 μm and 50x50 μm line features, but not for the remaining four Cu line features.

[0087] For the composition with the addition of 0.05 wt% dispersant and 0.1 wt% 35 mm PU beads (Comparison 1); Cu line dishing was significantly reduced across all six tested Cu line features compared to the other two compositions.

[0088] Effective reduction of Cu line dishing was obtained from the PIB-acting CMP composition using PU beads.

[0089] The results of Cu line dishing obtained from the composition at a DF of 1.5 psi and a slide speed of 1.0 m / s are shown in Table 3 and plotted in Figure 5.

Table 3

[0090] For the composition with the addition of only 0.05 wt% dispersant (Reference 1), Cu line dishing was reduced across all six tested Cu line features.

[0091] For the composition (Comparative Example 1) with the addition of 0.05% by mass of a dispersant and 0.1% by mass of 35 mm PU beads, Cu line dishing was significantly reduced across the tested Cu line features except for 1X1 μm.

Table 4

[0092] The effect of slide speeds of 0.6 m / s vs. 1.0 m / s at the same applied downward force of 1.5 psi on Cu line dishing across all six tested Cu line features was tested, and the results are shown in Table 4, Table 5, Table 6, and Figures 6, 7, and 8, respectively.

[0093] As a result shown in Table 4 and Figure 6, across all six tested Cu line features, Cu line dishing all increased and changed significantly when the slide speed increased from 0.6 m / s to 1.0 m / s.

Table 5

[0094] As a result shown in Table 5 and Figure 7, across all six tested Cu line features, Cu line dishing all decreased and changed significantly when the slide speed increased from 0.6 m / s to 1.0 m / s.

[0095] As a result shown in Table 6 and Figure 8, across all six tested Cu line features, Cu line dishing had very little change for the PIB - acting CMP composition containing 35 mm PU beads when the slide speed increased from 0.6 m / s to 1.0 m / s.

Table 6

[0096] Clearly, the PIB-acting CMP composition containing PU beads outperforms the Cu polishing composition without PU beads, providing a more stable over-polishing window against changes in slide speed.

[0097] Using three compositions, the Cu removal rate and Cu line dishing at a downward force of 1.5 psi and a slide speed of 0.6 m / s were obtained, compared, and the results are shown in Table 7.

Table 7

[0098] As a result shown in Table 7, compared with the Cu polishing composition without using PIB, the PIB-acting CMP composition containing PU beads not only increased the Cu removal rate by 11%, but also significantly reduced the Cu line dishing in the range of 31% - 43% across all six tested Cu line features.

[0099] The PIB technology was also shown to significantly reduce the lateral vibration of the wafer during polishing.

[0100] The embodiments of the present invention shown above, including the examples, are a number of exemplary embodiments that can be made from the present invention. It is contemplated that many other configurations of the process can be used and that the materials used in the process can be selected from many materials other than those specifically disclosed. The present disclosure also includes the following. Aspect 1 An abrasive; Polyurethane (PU) beads; A silicone-containing dispersant; Water; and Optionally, A chelating agent selected from the group consisting of amino acids and their derivatives, organic amines, and combinations thereof; A corrosion inhibitor; An organic quaternary ammonium salt; A biocide; A pH adjuster; An oxidizing agent A chemical mechanical polishing (CMP) composition comprising The CMP composition wherein the pH of the composition is 3.0 to 12.0; 5.5 to 7.5; or 6.0 to 7.5. Aspect 2 The abrasive is selected from the group consisting of colloidal silica; colloidal silica particles doped with other metal oxides within the lattice of colloidal silica; colloidal aluminum oxide selected from the group consisting of α-, β-, and γ-types of aluminum oxide; colloidal and photoactive titanium dioxide; cerium oxide; colloidal cerium oxide; inorganic metal oxide particles selected from the group consisting of alumina, titania, zirconia, and ceria; diamond particles; silicon nitride particles; monomodal, bimodal, or multimodal colloidal abrasive particles; flexible abrasive particles based on organic polymers; abrasive particles having a coated or modified surface; and combinations thereof; the abrasive is in the range of 0.0025 mass% to 25 mass%; 0.0025 mass% to 2.5 mass%; 0.005 mass% to 0.5 mass%; or 0.005 mass% to 0.15 mass%, the CMP composition according to Aspect 1 above. Aspect 3 The polyurethane (PU) beads have a size of 2 to 100 μm, 10 to 80 μm, 20 to 70 μm, or 30 to 50 μm, and the polyurethane (PU) beads are in the range of 0.01 mass% to 2.0 mass%, 0.025 mass% to 1.0 mass%, or 0.05 mass% to 0.5 mass%, the CMP composition according to Aspect 1 above. Aspect 4 The silicone-containing dispersant includes a silicone polyether containing both a water-insoluble silicone backbone and a water-soluble polyether pendant group, and the silicone-containing dispersant is in the range of 0.01 mass% to 2.0 mass%, 0.025 mass% to 1.0 mass%, or 0.05 mass% to 0.5 mass%, the CMP composition according to Aspect 1 above. Aspect 5 The CMP composition according to the above aspect 1, wherein the silicone-containing dispersant includes a silicone polyether containing a water-insoluble silicone skeleton and both a pendant group containing n repeating units (n is 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups. Aspect 6 The CMP composition includes a chelating agent selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and combinations thereof; the chelating agent is in the range of 0.1% by mass to 18% by mass; 0.5% by mass to 15% by mass; 1.0% by mass to 10.0% by mass; or 2.0% by mass to 10.0% by mass, the CMP composition according to the above aspect 1. Aspect 7 The CMP composition includes a corrosion inhibitor selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and tetrazole derivatives, and combinations thereof; the corrosion inhibitor is in the range of 0.005% by mass to 1.0% by mass; 0.01% by mass to 0.5% by mass; or 0.025% by mass to 0.25% by mass, the CMP composition according to the above aspect 1. Aspect 8 The CMP composition includes an abrasive selected from the group consisting of colloidal silica; colloidal silica particles doped with other metal oxides within the lattice of the colloidal silica; colloidal aluminum oxide selected from the group consisting of α-, β-, and γ-aluminum oxides; colloidal and photoactive titanium dioxide; cerium oxide; colloidal cerium oxide; inorganic metal oxide particles selected from the group consisting of alumina, titania, zirconia, and ceria; diamond particles; silicon nitride particles; monomodal, bimodal, or multimodal colloidal abrasive particles; flexible abrasive particles based on an organic polymer; abrasive particles with a coated or modified surface; and combinations thereof; The polyurethane (PU) beads have a size of 2 to 100 μm, 10 to 80 μm, 20 to 70 μm, or 30 to 50 μm; The silicone-containing dispersant includes a silicone polyether containing a water-insoluble silicone backbone and both pendant groups containing n repeating units (n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups; The chelating agent is selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and combinations thereof; The corrosion inhibitor is selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and tetrazole derivatives, and combinations thereof, of the CMP composition described in Aspect 1 above. Aspect 9 The CMP composition contains a biocide having an active ingredient selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and combinations thereof; the biocide is in the range of 0.0001% to 0.05% by mass; 0.0001% to 0.025% by mass; or 0.0001% to 0.01% by mass, and the CMP composition according to the above aspect 1. Aspect 10 The CMP composition contains an oxidizing agent selected from the group consisting of periodic acid, hydrogen peroxide, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and combinations thereof; the oxidizing agent is in the range of 0.1% to 10% by mass; 0.25% to 3% by mass; or 0.5% to 2.0% by mass, and the CMP composition according to the above aspect 1. Aspect 11 The CMP composition contains abrasive materials selected from the group consisting of colloidal silica; colloidal silica particles doped with other metal oxides within the lattice of colloidal silica; colloidal aluminum oxide selected from the group consisting of α-, β-, and γ-aluminum oxides; colloidal and photoactive titanium dioxide; cerium oxide; colloidal cerium oxide; inorganic metal oxide particles selected from the group consisting of alumina, titania, zirconia, and ceria; diamond particles; silicon nitride particles; monomodal, bimodal, or multimodal colloidal abrasive particles; flexible abrasive particles based on organic polymers; abrasive particles having a coated or modified surface; and combinations thereof; The polyurethane (PU) beads have a size of 2 to 100 μm, 10 to 80 μm, 20 to 70 μm, or 30 to 50 μm; The silicone-containing dispersant contains a silicone polyether containing both a water-insoluble silicone backbone and pendant groups containing n repeating units (n is 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups; The chelating agent is selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and combinations thereof; The oxidizing agent is selected from the group consisting of periodic acid, hydrogen peroxide, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and combinations thereof; The corrosion inhibitor is selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and tetrazole derivatives, and combinations thereof, and the CMP composition according to the above aspect 1. Aspect 12 The CMP composition contains an organic quaternary ammonium salt selected from the group consisting of choline salts having various counterions selected from the group consisting of choline bicarbonate, choline hydroxide, choline dihydrogen citrate salt, choline ethanolamine, choline bitartrate, and combinations thereof; the organic quaternary ammonium salt is in the range of 0.005% to 0.25% by mass, 0.001% to 0.05% by mass; or 0.002% to 0.01% by mass, and the CMP composition according to the above aspect 1. Aspect 13 The CMP composition includes an abrasive selected from the group consisting of colloidal silica; colloidal silica particles doped with other metal oxides within the lattice of colloidal silica; colloidal aluminum oxide selected from the group consisting of α-, β-, and γ-aluminum oxides; colloidal and photoactive titanium dioxide; cerium oxide; colloidal cerium oxide; inorganic metal oxide particles selected from the group consisting of alumina, titania, zirconia, and ceria; diamond particles; silicon nitride particles; monomodal, bimodal, or multimodal colloidal abrasive particles; flexible abrasive particles based on organic polymers; abrasive particles with coated or modified surfaces; and combinations thereof; The polyurethane (PU) beads have a size of 2 to 100 μm, 10 to 80 μm, 20 to 70 μm, or 30 to 50 μm; The silicone-containing dispersant includes a silicone polyether containing a water-insoluble silicone backbone and both pendant groups containing n repeating units (n is 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups; The chelating agent is selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and combinations thereof; The corrosion inhibitor is selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and tetrazole derivatives, and combinations thereof; the oxidizing agent is selected from the group consisting of periodic acid, hydrogen peroxide, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and combinations thereof; The CMP composition according to the above aspect 1, wherein the organic quaternary ammonium salt is selected from the group consisting of choline salts having various counterions selected from the group consisting of choline bicarbonate, choline hydroxide, choline dihydrogen citrate salt, choline ethanolamine, choline bitartrate, and combinations thereof. Aspect 14 The CMP composition is selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and combinations thereof that adjust the pH in the acidic direction, or sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkylammonium hydroxide, organic amines, and pH adjusters selected from the group consisting of combinations thereof that adjust the pH in the alkaline direction; the CMP composition has a pH of about 5.5 to about 9.0; about 6.0 to about 8.0; or about 6.0 to about 7.5. The CMP composition according to the above aspect 1. Aspect 15 The CMP composition according to the above aspect 1, comprising colloidal silica particles, a water-insoluble silicone backbone, and a silicone-containing dispersant containing both a pendent group containing n repeating units (n is 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups, and polyurethane (PU) beads. Aspect 16 The CMP composition as described in the above Aspect 1, comprising colloidal silica particles; a silicone-containing dispersant containing a silicone polyether containing a water-insoluble silicone backbone and pendant groups containing n repeating units (where n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups; polyurethane (PU) beads; a chelating agent selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, and combinations thereof; and a corrosion inhibitor selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and tetrazole derivatives, and combinations thereof. Aspect 17 The CMP composition as described in the above aspect 1 includes colloidal silica particles; a silicone-containing dispersant including a silicone polyether containing a water-insoluble silicone skeleton and pendant groups including n repeating units (where n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups; polyurethane (PU) beads; a chelating agent selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and combinations thereof; a corrosion inhibitor selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and tetrazole derivatives, and combinations thereof; and an oxidizing agent selected from the group consisting of periodic acid, hydrogen peroxide, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and combinations thereof. Aspect 18 The CMP composition as described in the above aspect 1 includes glycine, amitrole, ethylenediamine, choline bicarbonate, a biocide, colloidal silica particles, a silicone-containing dispersant including a silicone polyether containing a water-insoluble silicone skeleton and pendant groups including n repeating units (where n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups, and polyurethane (PU) beads. Aspect 19 The CMP composition according to aspect 1 above, comprising glycine, amitrole, ethylenediamine, choline bicarbonate, biocide, colloidal silica particles, a silicone-containing dispersant containing a water-insoluble silicone backbone and a silicone polyether containing both a pendant group containing n repeating units (where n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups, and polyurethane (PU) beads, and the CMP composition having a pH of 5.5 to 9.0. Aspect 20 The CMP composition according to aspect 1 above, comprising glycine, amitrole, ethylenediamine, choline bicarbonate, biocide, colloidal silica particles, a silicone-containing dispersant containing a water-insoluble silicone backbone and a silicone polyether containing both a pendant group containing n repeating units (where n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups, and polyurethane (PU) beads, and the CMP composition having a pH of 6.0 to 8.0. Aspect 21 Providing a semiconductor substrate having a surface containing copper or through-silicon via (TSV) copper; Providing a polishing pad; Providing a chemical mechanical polishing (CMP) composition according to any one of aspects 1 to 20 above; Contacting the surface of the semiconductor substrate with the polishing pad and the chemical mechanical polishing (CMP) composition; Polishing the surface containing the copper or TSV copper A method for chemically mechanically polishing a semiconductor substrate, comprising: Aspect 22 A semiconductor substrate having a surface containing copper or through-silicon via (TSV) copper; A polishing pad; A chemical mechanical polishing system comprising a chemical mechanical polishing (CMP) composition according to any one of aspects 1 to 20 above, where at least a part of the surface containing the copper or TSV copper is in contact with both the polishing pad and the chemical mechanical polishing composition.

Claims

1. A polishing abrasive, polyurethane (PU) beads; a silicone-containing dispersant; water; a chelating agent selected from the group consisting of amino acids and their derivatives, organic amines, and combinations thereof; and optionally, a corrosion inhibitor; an organic quaternary ammonium salt; a biocide; a pH adjuster; an oxidizing agent at least one selected from the group consisting of A chemical mechanical polishing (CMP) composition for chemically mechanically polishing a semiconductor substrate having a surface containing copper or through-silicon via (TSV) copper, comprising: The CMP composition, wherein the pH of the composition is 3.0 to 12.

0.

2. The polishing abrasive is colloidal silica; colloidal silica particles doped with other metal oxides within the lattice of colloidal silica; colloidal aluminum oxide selected from the group consisting of α-, β-, and γ-types of aluminum oxide; colloidal and photoactive titanium dioxide; cerium oxide; colloidal cerium oxide; inorganic metal oxide particles selected from the group consisting of alumina, titania, zirconia, and ceria; diamond particles; silicon nitride particles; monomodal, bimodal, or multimodal colloidal polishing abrasive particles; flexible polishing abrasive particles based on an organic polymer; polishing abrasive particles having a coated or modified surface; and polishing abrasive particles selected from the group consisting of combinations thereof; the polishing abrasive is in the range of 0.005% to 0.5% by mass, The CMP composition according to claim 1.

3. The polyurethane (PU) beads have a size of 10 to 80 μm, and the polyurethane (PU) beads are in the range of 0.025% to 1.0% by mass, The CMP composition according to claim 1.

4. The silicone-containing dispersant includes a silicone polyether containing both a water-insoluble silicone backbone and a water-soluble polyether pendant group, and the silicone-containing dispersant is in the range of 0.025% to 1.0% by mass, The CMP composition according to claim 1.

5. The CMP composition according to claim 1, wherein the silicone-containing dispersant contains a water-insoluble silicone skeleton and both a pendant group containing n repeating units (n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups, and the silicone-containing dispersant is in the range of 0.025% by mass to 1.0% by mass.

6. The CMP composition according to claim 1, wherein the CMP composition contains a chelating agent selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and combinations thereof; and the chelating agent is in the range of 0.5% by mass to 15% by mass.

7. The CMP composition according to claim 1, further comprising a corrosion inhibitor selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and tetrazole derivatives, and combinations thereof; and the corrosion inhibitor is in the range of 0.005% by mass to 1.0% by mass.

8. The CMP composition includes an abrasive selected from the group consisting of colloidal silica; colloidal silica particles doped with other metal oxides within the lattice of colloidal silica; colloidal aluminum oxide selected from the group consisting of α-, β-, and γ-aluminum oxides; colloidal and photoactive titanium dioxide; cerium oxide; colloidal cerium oxide; inorganic metal oxide particles selected from the group consisting of alumina, titania, zirconia, and ceria; diamond particles; silicon nitride particles; monomodal, bimodal, or multimodal colloidal abrasive particles; flexible abrasive particles based on organic polymers; abrasive particles with coated or modified surfaces; and combinations thereof; The polyurethane (PU) beads have a size of 10 to 80 μm; The silicone-containing dispersant includes a silicone polyether containing a water-insoluble silicone backbone and both pendant groups containing n repeating units (n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups; The chelating agent is selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and combinations thereof; The corrosion inhibitor is selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and tetrazole derivatives, and combinations thereof, for the CMP composition according to claim 1.

9. The CMP composition further comprises a biocide having an active ingredient selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and combinations thereof; the biocide is in the range of 0.0001% to 0.05% by mass. The CMP composition according to claim 1.

10. The CMP composition comprises an oxidizing agent selected from the group consisting of periodic acid, hydrogen peroxide, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and combinations thereof; the oxidizing agent is in the range of 0.1% to 10% by mass. The CMP composition according to claim 1.

11. The CMP composition comprises abrasive materials selected from the group consisting of colloidal silica; colloidal silica particles doped with other metal oxides within the lattice of colloidal silica; colloidal aluminum oxide selected from the group consisting of α-, β-, and γ-types of aluminum oxide; colloidal and photoactive titanium dioxide; cerium oxide; colloidal cerium oxide; inorganic metal oxide particles selected from the group consisting of alumina, titania, zirconia, and ceria; diamond particles; silicon nitride particles; monomodal, bimodal, or multimodal colloidal abrasive particles; flexible abrasive particles based on organic polymers; abrasive particles with coated or modified surfaces; and combinations thereof; The polyurethane (PU) beads have a size of 10 to 80 μm; The silicone-containing dispersant comprises a silicone polyether containing a water-insoluble silicone backbone and both pendant groups containing n repeating units (n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups; The chelating agent is selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, and combinations thereof; The oxidizing agent is selected from the group consisting of periodic acid, hydrogen peroxide, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and combinations thereof; The corrosion inhibitor is selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and tetrazole derivatives, and combinations thereof. The CMP composition according to claim 1.

12. The CMP composition includes an organic quaternary ammonium salt selected from the group consisting of choline salts having various counterions selected from the group consisting of choline bicarbonate, choline hydroxide, choline dihydrogen citrate salt, choline ethanolamine, choline bitartrate, and combinations thereof; the organic quaternary ammonium salt is in the range of 0.005% by mass to 0.25% by mass. The CMP composition according to claim 1.

13. The CMP composition includes an abrasive selected from the group consisting of colloidal silica; colloidal silica particles doped with other metal oxides within the lattice of the colloidal silica; colloidal aluminum oxide selected from the group consisting of α-, β-, and γ-aluminum oxides; colloidal and photoactive titanium dioxide; cerium oxide; colloidal cerium oxide; inorganic metal oxide particles selected from the group consisting of alumina, titania, zirconia, and ceria; diamond particles; silicon nitride particles; monomodal, bimodal, or multimodal colloidal abrasive particles; flexible abrasive particles based on an organic polymer; abrasive particles having a coated or modified surface; and combinations thereof; the polyurethane (PU) beads have a size of 10 to 80 μm; the silicone-containing dispersant includes a silicone polyether containing a water-insoluble silicone backbone and both pendant groups containing n repeating units (n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups; the chelating agent is selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and combinations thereof; the corrosion inhibitor is selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and tetrazole derivatives, and combinations thereof; The oxidizing agent is selected from the group consisting of periodic acid, hydrogen peroxide, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and combinations thereof; The CMP composition according to claim 1, wherein the organic quaternary ammonium salt is selected from the group consisting of choline bicarbonate, choline hydroxide, choline dihydrogen citrate salt, choline ethanolamine, choline bitartrate, and choline salts having various counterions selected from the group consisting of combinations thereof.

14. The CMP composition is selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and combinations thereof that adjust the pH in the acidic direction, or sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkylammonium hydroxide, organic amines, and combinations thereof that adjust the pH in the alkaline direction; the CMP composition has a pH of 5.5 to 9.0, the CMP composition according to claim 1.

15. The CMP composition according to claim 1, comprising colloidal silica particles; a silicone-containing dispersant comprising a silicone polyether containing a water-insoluble silicone backbone and both pendant groups containing n repeating units (n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups; polyurethane (PU) beads; at least two chelating agents selected from the group consisting of glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylamine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, 2,2-dimethyl-1,3-propanediamine, and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and combinations thereof; a corrosion inhibitor selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazole and tetrazole derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazole and tetrazole derivatives, and combinations thereof; and an oxidizing agent selected from the group consisting of periodic acid, hydrogen peroxide, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and combinations thereof.

16. The CMP composition according to claim 1, comprising glycine, amitrole, ethylenediamine, choline bicarbonate, a biocide, colloidal silica particles, a silicone-containing dispersant comprising a silicone polyether containing a water-insoluble silicone backbone and both pendant groups containing n repeating units (n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups, and polyurethane (PU) beads.

17. The CMP composition includes glycine, amitrole, ethylenediamine, choline bicarbonate, a biocide, colloidal silica particles, a water-insoluble silicone backbone, and a silicone-containing dispersant including a silicone polyether containing both a pendant group including n repeating units (n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups, and polyurethane (PU) beads, and the CMP composition has a pH of 5.5 to 9.0, the CMP composition according to claim 1.

18. The CMP composition includes glycine, amitrole, ethylenediamine, choline bicarbonate, a biocide, colloidal silica particles, a water-insoluble silicone backbone, and a silicone-containing dispersant including a silicone polyether containing both a pendant group including n repeating units (n is from 2 to 25) of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups, and polyurethane (PU) beads, and the CMP composition has a pH of 6.0 to 8.0, the CMP composition according to claim 1.

19. A step of providing a semiconductor substrate having a surface containing copper or through-silicon via (TSV) copper; A step of providing a polishing pad; A step of providing the chemical mechanical polishing (CMP) composition according to claim 1; A step of bringing the surface of the semiconductor substrate into contact with the polishing pad and the chemical mechanical polishing (CMP) composition; A step of polishing the surface containing the copper or TSV copper A method for chemically mechanically polishing a semiconductor substrate, including.

20. A semiconductor substrate having a surface containing copper or through-silicon via (TSV) copper; A polishing pad; A chemical mechanical polishing system including the chemical mechanical polishing (CMP) composition according to claim 1, The chemical mechanical polishing system, wherein at least a part of the surface containing the copper or TSV copper is in contact with both the polishing pad and the chemical mechanical polishing formulation.

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