Compositions and methods for CMP of metal films

Abstract

A chemical mechanical planarization composition for polishing molybdenum, comprising an aqueous liquid carrier, abrasive particles dispersed in the liquid carrier, an amine compound having an acid group selected from the group consisting of carboxylic acid, phosphoric acid, and sulfonic acid, and an oxidizing agent selected from the group consisting of hydrogen peroxide, ferric nitrate, potassium iodate, and mixtures thereof. A method for chemical mechanical polishing a substrate containing a molybdenum layer includes contacting the substrate with the polishing composition, moving the polishing composition relative to the substrate, and polishing the substrate to remove a portion of the molybdenum layer from the substrate.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 387,812, filed December 16, 2022, which is incorporated herein by reference. [Background technology]

[0002] The disclosed embodiments relate to chemical mechanical polishing of metal layers, and more particularly to compositions and methods for polishing metal layers that include molybdenum.

[0003] Chemical-mechanical polishing compositions use oxidizing agents, such as hydrogen peroxide, which can be chemically aggressive toward the metal being polished. At the advanced node of IC manufacturing, molybdenum is one of the promising metals to replace tungsten as a conductive contact to silicon devices to form integrated circuits. What is needed is a CMP slurry and process that polishes molybdenum without causing concomitant corrosion. Summary of the Invention

[0004] A chemical-mechanical polishing composition for polishing a substrate having a molybdenum layer is disclosed, which comprises, consists essentially of, or consists of an aqueous liquid carrier, abrasive particles dispersed in the liquid carrier, an amine compound having an acid group, and an oxidizing agent.

[0005] Also disclosed is a method for chemical-mechanical polishing a substrate including a molybdenum layer, which can include contacting the substrate with the polishing composition, moving the polishing composition relative to the substrate, and polishing the substrate to remove a portion of the molybdenum layer from the substrate, thereby polishing the substrate.

[0006] The pH of the CMP composition is in the range of 2.0 to 6.0, preferably 2.1 to 3.5, and the CMP composition is a stable composition.

[0007] Suitable abrasives include, but are not limited to, alumina, ceria, colloidal silica, high-purity colloidal silica with <1 ppm trace metals, titania, zirconia, metal-modified or composite particle abrasives such as iron-coated silica, silica-coated alumina, and combinations thereof. Colloidal silica particles and high-purity colloidal silica particles are preferred.

[0008] The abrasive particles have an average particle size in the range of 20 nm to 180 nm; 30 nm to 150 nm, 35 to 80 nm, or 40 to 75 nm.

[0009] The concentration of the abrasive ranges from 0.1 wt % to 20 wt %, preferably from about 0.1 wt % to about 10 wt %, more preferably from about 0.1 wt % to about 5 wt %, and most preferably from 0.1 wt % to 3 wt %; it is selected to adjust the film removal rate, particularly the dielectric film removal rate.

[0010] Suitable oxidizing agents include hydrogen peroxide, potassium iodate, ferric nitrate, and combinations thereof; the oxidizing agent ranges from 1 ppm to 100,000 ppm.

[0011] Hydrogen peroxide (H2O2) or potassium iodate are preferred oxidizing agents. In some embodiments, the oxidizing agents are hydrogen peroxide, potassium iodate, and ferric nitrate.

[0012] The oxidizing agent is typically present in an amount of from 1 ppm to 100,000 ppm by weight, preferably from 100 ppm to 50,000 ppm, more preferably from 5,000 ppm to 35,000 ppm.

[0013] The Mo corrosion inhibitor ranges from 0.01% to 10% by weight, preferably from 0.1% to 0.5% by weight, and most preferably from 0.1% to 0.3% by weight.

[0014] Inorganic acids such as nitric acid, sulfonic acid, or phosphoric acid are used as pH adjusters, and inorganic bases such as ammonium hydroxide, potassium hydroxide, or sodium hydroxide are also used as pH adjusters.

[0015] Suitable biocides include, but are not limited to, Kathon™ and Kathon™ CG / ICP II from Dow Chemical Co., which have the active ingredients 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.

[0016] The biocide is used in the range of 0.0001% to 0.05% by weight, preferably 0.0005% to 0.025% by weight, and more preferably 0.001% to 0.01% by weight.

[0017] Stabilizers can also be used at low pH. The stabilizer is optional. Stabilizers include, but are not limited to, organic carboxylic acids or organic carboxylic acid salts. Such stabilizers include, but are not limited to, malonic acid, citric acid, tartaric acid, lactic acid, oxalic acid, ascorbic acid, acetic acid, gluconic acid, and their sodium, potassium, and ammonium salts.

[0018] The stabilizer can be used in the range of 250 ppm to 10,000 ppm, more preferably in the range of 400 ppm to 5,000 ppm (or 0.04% to 0.5% by weight).

[0019] In another embodiment, a method for chemical mechanical polishing of a substrate comprising molybdenum is provided, the method comprising movably contacting a surface of the substrate with: a) an abrasive; and b) a liquid component comprising: water; an acid, preferably a mineral acid or a base, sufficient to provide a pH of 2 to 6, e.g., 2.1 to 3.5; and an oxidizer in the range of 1 ppm to 100,000 ppm, preferably 100 ppm to 50,000 ppm, more preferably 5,000 ppm to 35,000 ppm by weight, wherein in a preferred embodiment, the liquid component is deionized water and has a static etch rate of molybdenum of less than 100 angstroms / minute ("Å / min").

[0020] In another aspect, a method is provided for chemical mechanical polishing of a substrate comprising molybdenum; a dielectric layer, such as silicon oxide or silicon nitride; and a barrier film, such as TiN or Ti.

[0021] A method for chemical mechanical polishing a semiconductor substrate having a surface comprising molybdenum and at least one of a dielectric layer or a barrier layer includes the steps of: providing a semiconductor substrate; providing a polishing pad; providing the chemical mechanical polishing (CMP) composition disclosed above; contacting the surface of the semiconductor substrate with the polishing pad and the chemical mechanical polishing composition; and polishing the surface of the semiconductor, wherein the dielectric layer is a silicon oxide film or a silicon nitride film, and the barrier layer is selected from the group consisting of TiN, Ti, TaN, Ta, and combinations thereof.

[0022] The removal rate for molybdenum is greater than 1300, 1500, 2000 Å / min, or 2500 Å / min; the removal rate for dielectric layers is 15-200 Å / min; and the removal rate for barrier layers is 30-500 Å / min.

[0023] In one embodiment, the method includes a) movably contacting a surface having molybdenum thereon with an abrasive suspended in a liquid to form a slurry, the slurry comprising 0.1 to 20% by weight, e.g., 0.5 to 5% by weight, of the abrasive; the liquid comprising water; an acid or base sufficient to provide a pH of 2 to 6; an oxidizing agent in the range of 1 ppm to 100,000 ppm by weight, preferably 100 ppm to 50,000 ppm, more preferably 5,000 ppm to 35,000 ppm by weight; and an oxidizing agent in the range of 0.01 to 1,000 ppm by weight, preferably 0.1 to 100 ppm, more preferably 0.5 to 10 ppm, most preferably in the range of 1 to 5 ppm by weight; wherein the liquid is substantially free of fluoride-containing compounds, and polishing removes greater than 1,000 angstroms per minute (Å / min) of molybdenum and oxide films of various thicknesses. [Brief explanation of the drawings]

[0024] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter, and which are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and, together with the detailed description, serve to explain the principles of the disclosed subject matter.

[0025] [Figure 1] The relationship between the static etch rate (SER) of molybdenum and the molybdenum removal rate (RR) at 50°C is shown for different oxidants. DETAILED DESCRIPTION OF THE INVENTION

[0026] The present disclosure relates to Mo CMP bulk polishing compositions and systems used for chemical mechanical polishing of substrates containing molybdenum, silicon oxide (such as TEOS, PETEOS) or silicon nitride, and barrier films such as TiN, Ti, TaN, or Ta.

[0027] The Mo CMP polishing composition comprises an abrasive; a solvent selected from the group consisting of water, a water-miscible liquid, and combinations thereof; an amine compound having a carboxylic acid, phosphoric acid, or sulfonic acid; an oxidizing agent; a pH adjuster; and a biocide, and the pH of the CMP composition is in the range of 2.0 to 6.0, preferably 2.1 to 3.5.

[0028] Abrasives include, but are not limited to, alumina, ceria, colloidal silica, high purity colloidal silica with trace metal levels of <1 ppm, titania, zirconia, and combinations thereof.

[0029] Colloidal silica particles and high purity colloidal silica particles are preferred.

[0030] The abrasive particles may have any shape, such as spherical or cocoon-shaped.

[0031] High purity colloidal silica is prepared from TEOS or TMOS (due to its high purity), and such high purity colloidal silica particles have very low trace metal levels, typically at ppb levels, or very low ppm levels, e.g., <1 ppm.

[0032] The shape of the abrasive particles is measured by TEM or SEM techniques. The average abrasive size or particle size distribution can be measured by any suitable technique, such as by disk centrifugation (DC) or dynamic light scattering (DLS), using a colloidal dynamic method, or by a Malvern particle size analyzer.

[0033] The abrasive particles have an average particle size in the range of 20 nm to 180 nm; 30 nm to 150 nm, 35 to 80 nm, or 40 to 75 nm.

[0034] The CMP composition can use two or more different abrasives having different sizes.

[0035] The concentration of the abrasive ranges from 0.1 wt % to 20 wt %, preferably from about 0.1 wt % to about 10 wt %, more preferably from about 0.1 wt % to about 5 wt %, and most preferably from 0.1 wt % to 3 wt %; it is selected to adjust the film removal rate, particularly the dielectric film removal rate.

[0036] In some embodiments, the abrasive particles may comprise a high-purity colloidal silica dispersion, such as PL-3C (containing cationic cocoon-shaped silica particles) from Fuso Chemical Co., Ltd. The abrasive particles may be surface-modified, and in some embodiments, the abrasive particles are cationic or anionic. The abrasive may be PL-1, PL-1M, PL-2, PL-2C, PL-3, PL-7, or PL-2D from Fuso Chemical Co. Ltd.

[0037] The oxidizing agent is typically present in an amount of from 1 ppm to 100,000 ppm by weight, preferably from 100 ppm to 50,000 ppm, more preferably from 5,000 ppm to 35,000 ppm.

[0038] One problem with aggressive molybdenum slurries is that the molybdenum can be chemically attacked, for example, during rest periods when no polishing is taking place, i.e., when there is not enough abrasive movement to remove the oxide coating formed by the oxidizing system.

[0039] The Mo corrosion inhibitor ranges from 0.01 to 1000 ppm by weight, preferably from 0.1 to 100 ppm, more preferably from 0.5 to 10 ppm, and most preferably from 1 to 5 ppm by weight.

[0040] Inorganic acids such as nitric acid, sulfonic acid, or phosphoric acid are used as pH adjusters, and inorganic bases such as ammonium hydroxide, potassium hydroxide, or sodium hydroxide are also used as pH adjusters.

[0041] The choice of acid or base is not limited, so long as the strength of the acid or base is sufficient to give the slurry the desired pH in the range of 2-6.

[0042] Suitable biocides include, but are not limited to, Kathon™ and Kathon™ CG / ICP II from Dow Chemical Co., which have the active ingredients 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.

[0043] The biocide is used in the range of 0.0001% to 0.05% by weight; preferably 0.0005% to 0.025% by weight, more preferably 0.001% to 0.01% by weight.

[0044] The present disclosure provides methods of utilizing the disclosed CMP compositions for chemical mechanical planarization of molybdenum-containing substrates. In the semiconductor industry, the trend toward smaller and smaller feature sizes in the manufacture of integrated circuits has made minimizing or preventing dishing / erosion and plug recessing of features on semiconductor substrates, as well as the tunability of selectivity during CMP processing, increasingly important.

[0045] The solvent providing the majority of the liquid component can be water or a mixture of water and other liquids that are miscible with water. Examples of other liquids are alcohols such as methanol and ethanol. Advantageously, the solvent is water.

[0046] The slurry composition used in the method of the present disclosure is acidic and has a pH in the range of 2 to 6. Preferably, the pH is in the range of 2.1 to 3.5.

[0047] The wide pH range offers the advantage that the Mo:TEOS selectivity is highly tunable.

[0048] Stabilizers may also be used. At low pH, stabilizers are optional. Stabilizers include, but are not limited to, organic carboxylic acids or organic carboxylic acid salts. Such stabilizers include, but are not limited to, malonic acid, citric acid, tartaric acid, lactic acid, oxalic acid, ascorbic acid, acetic acid, gluconic acid, and their sodium, potassium, and ammonium salts.

[0049] The stabilizer can be used in the range of 250 ppm to 10,000 ppm, more preferably in the range of 400 ppm to 5,000 ppm (or 0.04% to 0.5% by weight).

[0050] The disclosed method involves the use of the aforementioned CMP compositions (as disclosed above) for chemical mechanical planarization of substrates comprising molybdenum and barriers such as TiN or Ti, TaN or Ta; and dielectric materials such as TEOS, PETOE, and low-k materials.

[0051] A method for chemical mechanical polishing a semiconductor substrate having a surface comprising molybdenum and at least one of a dielectric layer or a barrier layer includes the steps of: providing a semiconductor substrate; providing a polishing pad; providing the above-described chemical mechanical polishing (CMP) composition; contacting the surface of the semiconductor substrate with the polishing pad and the chemical mechanical polishing composition; and polishing the surface of the semiconductor, wherein the dielectric layer is an oxide film and the barrier layer is selected from the group consisting of TiN, Ti, TaN, Ta, and combinations thereof.

[0052] In a preferred embodiment, the polishing composition does not include a fluoride-containing compound.

[0053] In this method, a substrate (e.g., a wafer) is placed face-down against a polishing pad fixedly mounted on a rotatable platen of a CMP polisher. In this manner, the substrate to be polished and planarized is placed in direct contact with the polishing pad. A wafer carrier system or polishing head is used to hold the substrate in a fixed position and apply downward pressure against the backside of the substrate during the CMP process, rotating the platen and substrate. A polishing composition (slurry) is applied (usually continuously) onto the pad during the CMP process, causing material removal and planarizing the substrate.

[0054] In the disclosed method using the associated slurries, the molybdenum removal rate is at least greater than 1000 angstroms / min, and the TEOS removal rate ranges from less than 10 angstroms / min to greater than 500 angstroms / min, and these rates are maintained during chemical mechanical polishing when polishing is performed at a downforce of 2 psi. Higher removal rates are obtained with increasing downforce values.

[0055] As described above, an embodiment of the present disclosure is a composition for chemical mechanical polishing of a molybdenum-containing substrate. In one embodiment, the surface of the substrate, at least near the end of polishing, also has at least one feature thereon comprising a dielectric material. In one embodiment, the dielectric material is silicon oxide.

[0056] The removal selectivity of molybdenum to dielectrics is between 5 and 500, depending on the conditions of pH and abrasive type of the Mo CMP polishing composition of the invention herein.

[0057] The disclosed system involves the use of the aforementioned CMP compositions (as disclosed above) for chemical mechanical planarization of substrates composed of barriers such as molybdenum, TiN or Ti, TaN or Ta; and dielectric materials such as TEOS, silicon nitride materials.

[0058] In yet another aspect, a system is provided for chemical mechanical polishing of a substrate containing a surface comprising molybdenum and at least one of a dielectric layer, such as an oxide; and a barrier film, such as TiN or Ti, or TaN or Ta.

[0059] The system includes a substrate containing a surface comprising molybdenum, a dielectric layer such as an oxide, and at least one of a barrier film such as TiN or Ti or TaN or Ta; a polishing pad; and a chemical-mechanical polishing (CMP) composition disclosed above, wherein the surface of the semiconductor substrate is in contact with the polishing pad and the chemical-mechanical polishing composition.

[0060] In each of the above embodiments, the term "ppm" means parts per million by weight of the slurry (liquid plus abrasive), or of the liquid component if there is no abrasive suspended in the liquid.

[0061] A growing trend among CMP slurry suppliers is to reduce customer consumable costs by concentrating their products. The practice of providing concentrated slurries is becoming a requirement throughout the CMP industry. However, the level of concentration must be carefully selected so as not to compromise product stability and shelf life.

[0062] The inventors have found that even when using a slurry concentrate that minimizes organics (which can exacerbate long-term aging effects), the slurry concentrate still exhibits some effect on aging, particularly with respect to dishing and absolute molybdenum removal rate. Note that the slurry concentrate does not contain an oxidizer, which is added when the slurry concentrate is tank-mixed with water and an oxidizer to form the polishing slurry. It is known to adjust a slurry by adding various ingredients to the slurry. The present disclosure teaches a method of mixing two different slurry concentrates (conveniently referred to as a primary slurry concentrate and a secondary slurry concentrate) to standardize slurry performance with aging, where the mixing ratio of the slurry concentrates depends on the long-term aging of the primary slurry concentrate.

[0063] The formulations may be shipped in concentrated form and diluted by adding water at the time of use. The concentration of ingredients in the concentrate is increased according to the dilution factor at the time of use. In the illustrated embodiment, the dilution factor is about 2 to about 10, preferably about 3 to about 5.

[0064] Glossary CMP Methodology In the examples presented below, CMP experiments were performed using the following procedures and experimental conditions.

[0065] All percentages are by weight unless otherwise indicated.

[0066] component Colloidal silica: a first colloidal silica used as an abrasive having an average particle size of about 45 nanometers (nm); a second colloidal silica used as an abrasive having an average particle size of about 70 nanometers (nm);

[0067] Col Sil: Colloidal silica particles (various sizes) supplied by Fuso Chemical Inc., Japan. Parameters General Å or ​​A: Angstrom - unit of length BP: Back pressure, unit is psi CMP: Chemical mechanical planarization = chemical mechanical polishing CS: Carrier Speed DF: Downforce: Pressure applied during CMP, unit is psi min:minutes mL: milliliter mV: millivolt psi: pounds per square inch PS: Polishing tool platen rotation speed, in rpm (revolutions per minute) SF: Slurry flow rate, mL / min Wt%: Weight percentage (of listed ingredient) Mo:SiN selectivity: (Mo removal rate) / (SiN removal rate) TEOS:Mo selectivity: (TEOS removal rate) / (Mo removal rate)

[0068] Molybdenum removal rate: The molybdenum removal rate measured at a given down pressure. The down pressure of the CMP tool was 2.0 psi in the examples listed above.

[0069] Molybdenum films were measured using a ResMap COE, model 168, manufactured by Creative Design Engineering, Inc. (20565 Alves Dr., Cupertino, CA 95014). The ResMap tool is a four-point probe sheet resistance tool. 49 diameter scans with a 5 mm edge exclusion were performed on the molybdenum films.

[0070] CMP Tools The CMP tool used was a 300 mm Reflexion LK manufactured by Applied Materials, 3050 Boweres Avenue, Santa Clara, California, 95054. IC1010 pads supplied by DOW, Inc., 451 Bellevue Rd., Newark, DE 19713, were used for the blanket and patterned wafer studies.

[0071] The IC1000 or IC1010 pads were broken in by conditioning the pads for 10 minutes. The conditioner downforce was 5 pounds. [Example]

[0072] The present disclosure further includes the following examples.

[0073] Polishing experiments were performed using PVD-deposited molybdenum wafers. The blanket wafers were purchased from Advantiv. Film thickness specifications are summarized below: Mo: 5,000 Å PVD molybdenum.

[0074] Polishing experiment In the blanket wafer study, molybdenum blanket wafers and TEOS blanket wafers were polished under the standard conditions: table speed: 93 rpm, head speed: 87 rpm, film pressure: 2.0 psi, and slurry flow rate: 300 mL / min.

[0075] In the example formulations below, the abrasive particles were 1.0% by weight Fuso PL-3C.

[0076] It will be appreciated that the present disclosure includes numerous embodiments, including but not limited to the following.

[0077] Example 1 This example demonstrates the effectiveness of amino acids in reducing the static etch rate of molybdenum at an elevated temperature of 50°C. Sixteen compositions were prepared (Examples 1A, 1B, 1C, 1D, 1E, 1F, 1G, 1H, 1I, 1J, 1K, 1L, 1M, 1N, 1O, 1P). Each composition contained 0.08% by weight malonic acid and 1.0% by weight hydrogen peroxide at a pH of 2.3. The specific amino acids and concentrations used in each composition are listed in Table I.

[0078] The static etch rate of molybdenum in each of the 16 compositions was evaluated. A 2-inch square coupon wafer with a molybdenum layer was immersed (molybdenum side up) in each composition for 1 minute at 50°C. The molybdenum removal rate was determined by resistivity measurements taken before and after immersion in the composition.

[0079] As can be seen from the results in Table 1, the molybdenum etch rate was lower in the higher amino acid concentration of 0.5% compared to the 0.1% composition. It is clear that the molybdenum etch rate was lower in the compositions containing L-histidine, L-lysine, and L-arginine compared to the compositions containing glycine, L-valine, and L-serine. The relative Mo RR for 300 mm wafer polishing is shown in Table 1. The highest Mo RR reached 988 Å / min for composition 1B, and could be even higher at 1126 Å / min and 1037 Å / min for compositions 1K and 1O. [Table 1]

[0080] Example 2 This example demonstrates that the use of 0.75 wt.% ferric nitrate, an alternative oxidizer, instead of hydrogen peroxide can effectively reduce the static etch rate of molybdenum to less than 100 Å / min at a high temperature of 50°C, while the Mo RR from coupon wafer polishing can exceed 1300 Å / min. Sixteen compositions were prepared (Examples 2A, 2B, 2C, 2D, 2E, 2F, 2G, 2H, 2I, 2J, 2K, 2L, 2M, 2N, and 2O). Each composition contained 0.08 wt.% malonic acid and 1.0 wt.% hydrogen peroxide at a pH of 2.3. The specific amino acids and concentrations used in each composition are listed in Table II. [Table 2]

[0081] Example 3 This example demonstrates the effects of amine compounds with phosphoric acid, i.e., 2-aminoethyl phosphoric acid and 3-aminopropylphosphonic acid, and amine compounds with sulfonic acid, i.e., 3-amino-1-propanesulfonic acid and aminomethanesulfonic acid. Nine compositions were prepared (Examples 3A, 3B, 3C, 3D, 3E, 3F, 3G, 3H, and 3I). Each composition contained 0.08 wt. % malonic acid and 1.0 wt. % hydrogen peroxide at pH 2.3. The specific amino acids and concentrations used in each composition are listed in Table III. The static etch rate of molybdenum at elevated temperatures of 50°C can be reduced to less than 100 Å / min with amino phosphoric acid concentrations greater than 0.35% and 0.5%, e.g., for 3C and 3E, respectively. The Mo static etch rate of amino sulfonic acids, i.e., Examples 3G and 3I, did not decrease as significantly as that of amino phosphoric acid, but was still lower than that of the control, Example 3A, as shown in Table III. [Table 3]

[0082] Example 4

[0083] This example demonstrates the combination of various amino acids, glycine, and L-histidine with oxidizers, hydrogen peroxide, potassium iodate, and ferric nitrate, for both Mo static etch rates and 300 mm Mo removal rates. Twelve compositions were prepared (Examples 4A, 4B, 4C, 4D, 4E, 4F, 4G, 4H, 4I, 4J, and 4K). Each composition contained 0.08 wt. % malonic acid and 1.0 wt. % hydrogen peroxide at a pH of 2.3. The specific amino acids, oxidizers, and their relative concentrations used in each composition are listed in Table IV. For compositions 4F and 4G, which contained potassium iodate as the oxidizer, the Mo static etch rate at 50°C could be significantly reduced to less than 50 Å / min, while the Mo removal rate exceeded 800 Å / min. Compositions 4H and 4J, which contain ferric nitrate as the oxidizer, have even lower Mo static etch rates, but still relatively low Mo removal rates of about 690-650 Å / min, respectively. [Table 4]

[0084] Figure 1 shows the relationship between static etch rates of molybdenum and molybdenum removal rates at 50°C for different oxidizers: (1) HO, (2) oxidizer B: KIO, and (3) oxidizer C: Fe(NO) Of the three oxidizers used in the disclosed compositions (1A-4K), the HO-based formulations generally produced higher static etch rates of Mo at 50°C. The KIO formulations generally produced lower static etch rates and higher Mo removal rates than the HO formulations. The Fe(NO) based formulations generally produced lower static etch rates and higher Mo removal rates than the HO and KIO formulations.

[0085] In some embodiments, the Mo RR is about 500 to about 2000 Å / min. In some embodiments, the SiN RR is about 1 to about 50 Å / min. In some embodiments, the Mo to SiN removal rate selectivity is about 500:1 to about 5:1, more preferably about 400:1 to about 10:1.

[0086] In some embodiments, the RR of TEOS is about 50 to about 400 Å / min. In some embodiments, the removal rate selectivity of Mo to TEOS is about 1:1 to about 50:1, more preferably about 1:1 to about 10:1.

[0087] In some embodiments, the chemical-mechanical polishing composition does not contain an anionic polymer or an anionic surfactant.

[0088] In some embodiments, the chemical-mechanical polishing composition contains a cationic surfactant. In an exemplary embodiment, the cationic surfactant is JEFFAMINE® T-403 (a polyetheramine). JEFFAMINE® T-403 (CAS No. 39423-51-3) is characterized by an oxypropylene repeat unit in the main chain. JEFFAMINE T-403 is a trifunctional primary amine with an average molecular weight of about 440. The amine group is located on a secondary carbon atom at the end of an aliphatic polyether chain.

[0089] In a first embodiment, the composition may comprise, consist of, or consist essentially of a chemical mechanical polishing composition comprising an aqueous liquid carrier; abrasive particles dispersed in the liquid carrier; an amine compound having an acid group; and an oxidizing agent.

[0090] A second embodiment may include the first embodiment, wherein the oxidizing agent is selected from hydrogen peroxide, ferric nitrate monohydrate, and potassium iodate oxidizing agents, and mixtures thereof.

[0091] In the illustrated embodiment, the second chemical additive includes potassium iodate and the third chemical additive includes malonic acid.

[0092] A third embodiment may include any one of the first and second embodiments, wherein the composition further includes a carboxylic acid as a stabilizer that forms a complex with the ferric ion.

[0093] A fourth embodiment can include any one of the first to third embodiments, wherein the amine compound is selected from the group consisting of a carboxylic acid, a phosphoric acid, and a sulfonic acid.

[0094] A fifth embodiment may include any one of the first through fourth embodiments, wherein the amine compound includes one or more amino acids from the group consisting of α-amino acids, glycine, L-histidine, L-lysine, L-arginine, β-amino acids, β-alanine, and mixtures thereof. In an exemplary embodiment, the first chemical additive includes L-histidine and glycine. In a further embodiment, the first chemical additive is L-histidine and the second chemical additive is KIO.

[0095] A sixth embodiment may include any one of the first through fifth embodiments, wherein the amine compound is an amino phosphate selected from the group consisting of (aminomethyl)phosphate, (2-aminoethyl)phosphate, and (3-aminoethyl)phosphate, and mixtures thereof.

[0096] A seventh embodiment can include any one of the first through sixth embodiments, wherein the amine compound is an aminosulfonic acid selected from the group consisting of aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 3-amino-1-propanesulfonic acid, and mixtures thereof.

[0097] An eighth embodiment can include any one of the first through seventh embodiments, wherein the abrasive particles include cationic or anionic silica, zirconia, and alumina.

[0098] In a ninth embodiment, a method for chemically mechanically polishing a substrate having a molybdenum layer may include, consist of, or consist essentially of: (a) contacting the substrate with any one of the first through eighth polishing composition embodiments; (b) moving the polishing composition relative to the substrate; and (c) polishing the substrate to remove a portion of the molybdenum layer or the molybdenum layer from the substrate, thereby polishing the substrate.

[0099] The embodiments listed above, including the working examples, are examples of many embodiments that may result from the present disclosure. It is contemplated that many other configurations of the process may be used and that the materials used in the process may be selected from many materials other than those specifically disclosed.

Claims

1. 1. A chemical-mechanical polishing composition comprising: 0.1% to 20%, preferably 0.1% to 10%, more preferably 0.1% to 5%, and most preferably 0.1% to 3% by weight of abrasive particles; 0.01 wt % to 10.0 wt %, preferably 0.1 wt % to 8.0 wt %, or most preferably 1 wt % to 5 wt % of a first chemical additive, said first chemical additive comprising an amine compound, said amine compound further comprising a carboxylic acid, or a phosphoric acid, or a sulfonic acid; 0.01 to 0.2 wt. %, or preferably 0.01 to 0.05 wt. %, of a second chemical additive that is an oxidizer selected from the group consisting of hydrogen peroxide, ferric nitrate, potassium iodate, and mixtures thereof; an aqueous solvent; Optionally, Biocides, and A pH adjuster; Including, the chemical-mechanical polishing composition has a pH of 2 to 7, preferably 2 to 5, more preferably 2 to 4, and most preferably 2 to 3.5; Chemical mechanical polishing composition.

2. 2. The chemical mechanical polishing composition of claim 1, wherein the abrasive particles are selected from alumina, ceria, colloidal silica, high purity colloidal silica with trace metals of <1 ppm, titania, zirconia, metal-modified or composite particle abrasives such as iron-coated silica, silica-coated alumina, and combinations thereof.

3. 2. The chemical mechanical polishing composition of claim 1, wherein the amine compound comprises one or more amino acids selected from the group consisting of α-amino acids, glycine, L-histidine, L-lysine, L-arginine, β-amino acids, β-alanine, and mixtures thereof.

4. 2. The chemical mechanical polishing composition of claim 1, wherein the amine compound is an aminophosphate selected from the group consisting of (aminomethyl)phosphate, (2-aminoethyl)phosphate, and (3-aminoethyl)phosphate, and mixtures thereof.

5. 2. The chemical-mechanical polishing composition of claim 1, wherein the amine compound is an aminosulfonic acid selected from the group consisting of aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 3-amino-1-propanesulfonic acid, and mixtures thereof.

6. The chemical-mechanical polishing composition of claim 1 , wherein the oxidizing agent is ferric nitrate or potassium iodate.

7. 10. The chemical-mechanical polishing composition of claim 1, wherein the static etching rate of molybdenum at 50°C is less than 100 Å / min, more preferably less than 50 Å / min.

8. 10. The chemical-mechanical polishing composition of claim 1, wherein the abrasive particles comprise surface-modified colloidal silica, preferably cationic colloidal silica or anionic colloidal silica.

9. the chemical-mechanical polishing composition contains a cationic surfactant; or The chemical-mechanical polishing composition of claim 1 , wherein the chemical-mechanical polishing composition does not contain an anionic polymer or an anionic surfactant.

10. 1. A chemical-mechanical polishing composition comprising: 0.1% to 10%, preferably 0.1% to 5%, more preferably 0.1% to 3%, and most preferably 0.5% to 2% by weight of abrasive particles; 0.01 wt % to 10.0 wt %, preferably 0.05 wt % to 5.0 wt %, or most preferably 0.1 wt % to 1 wt % of a first chemical additive, said first chemical additive comprising an amine compound, said amine compound further comprising a carboxylic acid, or a phosphoric acid, or a sulfonic acid; 0.01 to 0.0 wt. %, or preferably 0.01 to 0.5 wt. %, of a second chemical additive that is an oxidizer selected from the group consisting of ferric nitrate, potassium iodate, and mixtures thereof; an aqueous solvent; Optionally, Biocides, and A pH adjuster; Including, the chemical-mechanical polishing composition has a pH of 2 to 7, preferably 2 to 5, more preferably 2 to 4, and most preferably 2 to 3.5; The chemical mechanical polishing composition does not contain hydrogen peroxide. Chemical mechanical polishing composition.

11. 11. The chemical mechanical polishing composition of claim 10, wherein the amine compound comprises one or more amino acids selected from the group consisting of α-amino acids, glycine, L-histidine, L-lysine, L-arginine, β-amino acids, β-alanine, and mixtures thereof.

12. 11. The chemical-mechanical polishing composition of claim 10, wherein the amine compound is an aminophosphate selected from the group consisting of (aminomethyl)phosphate, (2-aminoethyl)phosphate, and (3-aminoethyl)phosphate, and mixtures thereof.

13. 11. The chemical-mechanical polishing composition of claim 10, wherein the amine compound is an aminosulfonic acid selected from the group consisting of aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 3-amino-1-propanesulfonic acid, and mixtures thereof.

14. 11. The chemical mechanical polishing composition of claim 10, wherein the ratio of the first chemical additive to the second chemical additive is from about 10:1 to about 1:10, preferably from about 3:1 to about 1:3, and most preferably from about 2:1 to about 1:

2.

15. The chemical mechanical polishing composition of any one of claims 1 to 14, having a static etching rate of molybdenum at 50°C of less than 200 Å / min, preferably less than 100 Å / min, and more preferably less than 75 Å / min.

16. 1. A method for chemical mechanical polishing (CMP) a semiconductor substrate having at least one surface comprising a molybdenum-containing film, comprising: providing the semiconductor substrate; providing a polishing pad; Providing a chemical mechanical polishing (CMP) composition according to any one of claims 1 to 15; contacting the surface of the semiconductor substrate with the polishing pad and the chemical-mechanical polishing composition; and polishing said at least one surface; A method comprising:

17. 17. The method of claim 16, wherein the semiconductor substrate further comprises a silicon oxide film, the silicon oxide film being selected from the group consisting of a chemical vapor deposition (CVD) silicon oxide film, a plasma-enhanced CVD (PECVD) silicon oxide film, a high-density deposition CVD (HDP) silicon oxide film, or a spin-on silicon oxide film.

18. The silicon oxide film is SiO ２ 18. The method of claim 17, wherein the membrane has a molybdenum:silicon oxide removal selectivity of greater than 10, preferably greater than 30, more preferably greater than 50.

19. a Mo to SiN removal rate selectivity of about 500:1 to about 5:1; or 17. The method of claim 16, wherein the molybdenum:silicon oxide removal selectivity is greater than 5, preferably greater than 50, and more preferably greater than 500.

20. 1. A system for chemical mechanical polishing (CMP) a semiconductor substrate having at least one surface comprising a molybdenum-containing film, comprising: a. the semiconductor substrate; b. The chemical-mechanical polishing (CMP) composition of any one of claims 1 to 15; c. a polishing pad; Including, The at least one surface comprising molybdenum is in contact with the polishing pad and the chemical-mechanical polishing composition.

Images