Compositions and methods for CMP of metal films

Abstract

A chemical mechanical planarization composition for polishing molybdenum comprising an aqueous-based liquid carrier; abrasive particles dispersed in the liquid carrier; an amine compound having an acid group selected from 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 of a substrate comprising a molybdenum layer comprises contacting the substrate with the above polishing composition; moving the polishing composition relative to the substrate; and grinding the substrate to remove a portion of the molybdenum layer from the substrate.

Description

[0001] Related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 387,812, filed December 16, 2022, which is incorporated herein by reference in its entirety. Background Art

[0003] The disclosed embodiments relate to chemical mechanical polishing of metal layers, and more particularly to compositions and methods for polishing metal layers containing molybdenum.

[0004] Chemical mechanical polishing compositions utilize an oxidizing agent, such as hydrogen peroxide, which can be chemically aggressive to the metal being polished.In advanced nodes of IC manufacturing, molybdenum is one of the promising metals to replace tungsten as the conductive contact to silicon devices to form integrated circuits.

[0005] A need exists for CMP slurries and processes that polish molybdenum without causing corresponding corrosion. Summary of the Invention

[0006] A chemical mechanical polishing composition for polishing a substrate having a molybdenum layer is disclosed. The polishing composition comprises, consists essentially of, or consists of a water-based liquid carrier, abrasive particles dispersed in the liquid carrier, an amine compound having an acid group, and an oxidizing agent.

[0007] Further disclosed is a method for chemically mechanically polishing a substrate comprising a molybdenum layer. The method may include contacting the substrate with the polishing composition, moving the polishing composition relative to the substrate, and grinding the substrate to remove a portion of the molybdenum layer from the substrate, thereby polishing the substrate.

[0008] The pH of the CMP composition ranges from 2.0 to 6.0, preferably from 2.1 to 3.5, and the CMP composition is a stable composition.

[0009] 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 and high purity colloidal silica particles are preferred.

[0010] The abrasive particles have an average particle size ranging from 20 nm to 180 nm, from 30 nm to 150 nm, from 35 nm to 80 nm, or from 40 nm to 75 nm.

[0011] The concentration of the abrasive ranges from 0.1 wt% to 20 wt%, preferably 0.1 wt% to 10 wt%, more preferably 0.1 wt% to 5 wt%, and most preferably 0.1 wt% to 3 wt%; it is selected to adjust the film removal rate, especially the dielectric film removal rate.

[0012] Suitable oxidizing agents include hydrogen peroxide, potassium iodate, ferric nitrate, and combinations thereof; and the range of the oxidizing agent is 1 ppm to 100,000 ppm.

[0013] Hydrogen peroxide (H2O2) or potassium iodate are preferred oxidizing agents. In some embodiments, the oxidizing agent is hydrogen peroxide, potassium iodate and ferric nitrate.

[0014] The oxidizing agent is typically present in an amount 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).

[0015] The range of corrosion inhibitor for Mo is 0.01 wt% to 10 wt%, preferably 0.1 wt% to 0.5 wt%, most preferably 0.1 wt% to 0.3 wt%;

[0016] An inorganic acid such as nitric acid, sulfonic acid, or phosphoric acid is used as a pH adjuster, and an inorganic base such as ammonium hydroxide, potassium hydroxide, or sodium hydroxide is also used as a pH adjuster.

[0017] Suitable biocides include, but are not limited to, Kathon™ and Kathon™ CG / ICP II from Dow Chemical Co. The active ingredients are 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.

[0018] The biocide is used in the range of 0.0001 wt% to 0.05 wt%; preferably 0.0005 wt% to 0.025 wt%, more preferably 0.001 wt% to 0.01 wt%.

[0019] Stabilizers can also be used at low pH. Stabilizers are optional. Stabilizers include, but are not limited to, organic carboxylic acids or organic carboxylate salts. These 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.

[0020] The stabilizer may 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 wt% to 0.5 wt%).

[0021] In another embodiment, a method of chemical mechanical polishing of a substrate comprising molybdenum is provided, the method comprising: removably contacting the surface of the substrate with a) an abrasive and b) a liquid component comprising water; an acid, preferably an inorganic acid or a base, sufficient to provide a pH of 2 to 6 (e.g., 2.1 to 3.5); an oxidizing agent 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 wherein the static etch rate of the molybdenum is less than 0.05 t / min.

[0022] In another aspect, a method of chemical mechanical polishing a substrate comprising molybdenum; a dielectric layer, such as silicon oxide or silicon nitride; and a barrier film, such as TiN or Ti, is provided.

[0023] A method for chemical mechanical polishing of a semiconductor substrate comprising a molybdenum-containing surface and at least one dielectric layer or barrier layer comprises the steps of providing a semiconductor substrate; providing a polishing pad; providing a chemical mechanical polishing (CMP) composition as 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 or silicon nitride film, and the barrier layer is selected from TiN, Ti, TaN, Ta, and combinations thereof.

[0024] The removal rate of molybdenum is greater than 1300, 1500, or The dielectric layer removal rate is 15 to The barrier layer removal rate is 30 to

[0025] In one embodiment, the method comprises removably contacting a surface having molybdenum thereon with a) an abrasive material suspended in a liquid to form a slurry, said slurry comprising: 0.1-20 wt. %, e.g., 0.5-5 wt. % of said abrasive material; said 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, preferably 100 ppm to 50,000 ppm, more preferably 5,000 ppm to 35,000 ppm (by weight); and 0.01 to 1,000 ppm, preferably 0.1 to 100 ppm, more preferably 0.5 to 10 ppm; most preferably 1 to 5 ppm (by weight); said liquid being substantially free of fluorine-containing compounds, wherein polishing removes greater than of molybdenum and oxide films of different thicknesses. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter. In the drawings:

[0027] Figure 1 Molybdenum static etch rate and Mo removal rate at 50°C are illustrated for different oxidants. DETAILED DESCRIPTION

[0028] The present disclosure relates to Mo CMP bulk polishing compositions and systems for chemical mechanical polishing of substrates comprising molybdenum, silicon oxide (eg, TEOS, PETEOS), or silicon nitride, and a barrier film (eg, TiN, Ti, TaN, or Ta).

[0029] The Mo CMP polishing composition comprises: an abrasive; a solvent selected from water, a water-miscible liquid and a combination thereof; an amine compound having a carboxylic acid, a phosphoric acid or a sulfonic acid; an oxidizing agent; a pH adjuster; and a biocide; wherein the pH range of the CMP composition is 2.0 to 6.0, preferably 2.1 to 3.5.

[0030] Abrasives include, but are not limited to, alumina, ceria, colloidal silica, high purity colloidal silica with trace metal content <1 ppm, titania, zirconia, and combinations thereof.

[0031] Preferred are colloidal silica and high-purity colloidal silica particles.

[0032] The abrasive particles may have any shape, such as a spherical shape or a cocoon shape.

[0033] High purity colloidal silica is prepared from TEOS or TMOS (due to its high purity). Such high purity colloidal silica particles have very low trace metal levels, typically ppb levels or very low ppm levels, such as <1 ppm.

[0034] The abrasive particle shape is measured by TEM or SEM methods.The average abrasive size or particle size distribution can be measured by using any suitable technique, such as disc centrifugation (DC), dynamic light scattering (DLS), colloid dynamics, or by Malvern particle size analyzer.

[0035] The abrasive particles have an average particle size in the range of 20 nm to 180 nm; 30 nm to 150 nm, 35 nm to 80 nm, or 40 nm to 75 nm.

[0036] The CMP composition may utilize two or more abrasives of different sizes.

[0037] The concentration of the abrasive ranges from 0.1 wt% to 20 wt%, preferably 0.1 wt% to 10 wt%, more preferably 0.1 wt% to 5 wt%, and most preferably 0.1 wt% to 3 wt%; it is selected to adjust the film removal rate, especially the dielectric film removal rate.

[0038] In some embodiments, the abrasive particles may comprise a high-purity colloidal silica dispersion, such as PL-3C (comprising 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.

[0039] The oxidizing agent is typically present in an amount 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).

[0040] One problem with aggressive molybdenum slurries is that their chemistry can attack the molybdenum during idle periods, such as when there is no polishing (that is, no abrasive movement sufficient to remove the oxide coating formed by the oxidation system).

[0041] The range of the corrosion inhibitor for Mo is 0.01-1000 ppm, preferably 0.1-100 ppm, more preferably 0.5-10 ppm (by weight); most preferably 1-5 ppm (by weight).

[0042] An inorganic acid such as nitric acid, sulfonic acid, or phosphoric acid is used as a pH adjuster, and an inorganic base such as ammonium hydroxide, potassium hydroxide, or sodium hydroxide is also used as a pH adjuster.

[0043] The choice of acid or base is not limited, so long as the acid or base is strong enough to provide the slurry with the desired pH in the range of 2-6.

[0044] Suitable biocides include, but are not limited to, Kathon™ and Kathon™ CG / ICP II from Dow Chemical Co. The active ingredients are 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.

[0045] The biocide is used in the range of 0.0001 wt% to 0.05 wt%; preferably 0.0005 wt% to 0.025 wt%, more preferably 0.001 wt% to 0.01 wt%.

[0046] The present disclosure provides a method for chemical mechanical planarization of molybdenum-containing substrates using the disclosed CMP compositions. As the semiconductor industry moves toward smaller and smaller feature sizes in integrated circuit fabrication, minimizing or preventing recessing / erosion and plug recessing of features on semiconductor substrates and selective adjustability during CMP processing become increasingly important.

[0047] The solvent providing the major portion of the liquid component may be water or a mixture of water and other liquids miscible with water. Examples of other liquids are alcohols, such as methanol and ethanol. Advantageously, the solvent is water.

[0048] 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 range is 2.1 to 3.5.

[0049] The wide pH range provides the advantage of highly tunable Mo:TEOS selectivity.

[0050] Stabilizers may also be used. At low pH, stabilizers are optional. Stabilizers include, but are not limited to, organic carboxylic acids or organic carboxylate salts. These 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.

[0051] The stabilizer may be used in the range of 250 ppm to 10,000 ppm, more preferably 400 ppm to 5,000 ppm (or 0.04 wt% to 0.5 wt%).

[0052] The method of the present disclosure requires the use of the aforementioned CMP composition (as disclosed above) for chemical mechanical planarization of substrates containing molybdenum, barrier layers such as TiN or Ti, TaN or Ta; and dielectric materials such as TEOS, PETOES, and low-k materials.

[0053] A method for chemical mechanical polishing of a semiconductor substrate comprising a molybdenum-containing surface and at least one dielectric layer or barrier layer comprises the steps of providing a semiconductor substrate; providing a polishing pad; providing a 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 an oxide film and the barrier layer is selected from TiN, Ti, TaN, Ta, and combinations thereof.

[0054] And in a preferred embodiment, the polishing composition contains no fluorine-containing compounds.

[0055] In this method, a substrate (e.g., a wafer) is placed face-down on a polishing pad that is fixedly attached to a rotatable platen of a CMP polishing machine. In this way, 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 place and apply downward pressure to the backside of the substrate while rotating the platen and substrate during the CMP process. During the CMP process, a polishing composition (slurry) is applied (usually continuously) to the polishing pad to effect material removal and planarize the substrate.

[0056] In the disclosed methods using the relevant slurries, the removal rates for molybdenum were at least greater than 1000 angstroms / minute, and the removal rates for TEOS ranged from less than 10 angstroms / minute to greater than 500 angstroms / minute, when polishing at a downward force of 2 psi. These were maintained during their chemical mechanical polishing. Higher removal rates were achieved as the downward force values ​​were increased.

[0057] As indicated above, embodiments of the present disclosure are compositions for chemical mechanical polishing of molybdenum-containing substrates. In one embodiment, at least near the end of polishing, the substrate surface also has at least one feature thereon comprising a dielectric material. In one embodiment, the dielectric material is silicon oxide.

[0058] The removal selectivity of molybdenum relative to dielectrics ranges from 5 to 500, depending on the pH and type of abrasive conditions of the Mo CMP polishing compositions of the invention herein.

[0059] The disclosed system requires the use of the aforementioned chemical mechanical polishing composition (as disclosed above) for chemical mechanical planarization of substrates comprising molybdenum, a barrier layer such as TiN or Ti, TaN or Ta; and a dielectric material such as TEOS, silicon nitride material.

[0060] In yet another aspect, a system for chemical mechanical polishing of a substrate comprising a molybdenum-containing surface and at least one dielectric layer (eg, oxide); and a barrier film, such as TiN or Ti or TaN or Ta, is provided.

[0061] The system comprises: a substrate comprising a molybdenum-containing surface and at least one dielectric layer (e.g., an oxide); and a barrier film (e.g., TiN or Ti or TaN or Ta); a polishing pad; a chemical mechanical polishing (CMP) composition as disclosed above; and wherein the surface of the semiconductor substrate is in contact with the polishing pad and the chemical mechanical polishing composition.

[0062] In the above embodiments, the term "ppm" refers to parts per million by weight of the slurry (liquid plus abrasive) or the liquid component (if there is no suspended abrasive in the liquid).

[0063] Among CMP slurry suppliers, there is a growing trend toward reducing consumable costs for consumers by concentrating their products. Providing concentrated slurries is becoming a requirement within the CMP industry. However, the concentration level must be carefully selected to avoid compromising product stability and shelf life.

[0064] It was found that even with a slurry concentrate that minimizes organic matter (which can exacerbate long-term aging effects), the slurry concentrate still exhibited some effect on aging, particularly with respect to dishing and absolute molybdenum removal rate. It should be noted that the slurry concentrate did not contain an oxidizing agent, which is added when the slurry concentrate is tank-mixed with water and an oxidizing agent to form a polishing slurry. It is known to adjust a slurry by adding various components thereto. The present disclosure teaches a method of mixing two different slurry concentrates (referred to as a primary slurry concentrate and a secondary slurry concentrate for convenience), wherein the mixing ratio of the slurry concentrates depends on the long-term aging of the primary slurry concentrate, in order to normalize the slurry's resistance to aging.

[0065] The formulation can be shipped in concentrated form and diluted by adding water when used. The concentration of the components in the concentrate increases according to the dilution factor when used. In the embodiment shown, the dilution factor is between about 2x and about 10x, preferably between about 3x and about 5x.

[0066] Glossary

[0067] CMP Method

[0068] In the examples presented below, CMP experiments were conducted using the procedures and experimental conditions given below.

[0069] Unless otherwise indicated, all percentages are by weight.

[0070] Components

[0071] 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);

[0072] Col Sil: colloidal silica particles (with different sizes) supplied by Fuso Chemical Inc., Japan.

[0073] parameter

[0074] generally

[0075] or A: Angstrom - unit of length

[0076] BP: back pressure, unit psi

[0077] CMP: Chemical Mechanical Planarization = Chemical Mechanical Polishing

[0078] CS: Carrier speed

[0079] DF: Downward force: The pressure applied during CMP, in psi

[0080] min: minutes

[0081] ml: milliliters

[0082] mV: millivolt

[0083] psi: pounds per square inch

[0084] PS: The platen rotation speed of the polishing equipment, unit rpm (revolutions per minute)

[0085] SF: slurry flow rate, ml / min

[0086] Weight %: weight percentage (of the listed components)

[0087] Mo:SiN selectivity: (Mo removal rate) / (SiN removal rate)

[0088] TEOS:Mo selectivity: (TEOS removal rate) / (Mo removal rate)

[0089] Molybdenum removal rate: The molybdenum removal rate measured at a given downforce. In the above examples, the downforce of the CMP apparatus was 2.0 psi.

[0090] The molybdenum films were measured using a ResMap COE (Model 168) manufactured by Creative Design Engineering, Inc., 20565 Alves Dr., Cupertino, CA, 95014. The ResMap instrument is a four-point probe sheet resistance tool. A 49-point diameter scan (5 mm edge exclusion) was performed on the molybdenum film.

[0091] CMP equipment

[0092] The CMP equipment used was a 300 mm Reflexion LK manufactured by Applied Materials, 3050 Bowers Avenue, Santa Clara, California, 95054. IC1010 pads supplied by DOW, Inc., 451 Bellevue Rd., Newark, DE 19713 were used for blanket and patterned wafer studies.

[0093] The IC1000 or IC1010 pads were broken in by conditioning the pads on a conditioner with 5 lbs down pressure for 10 minutes.

[0094] Working Examples

[0095] The present disclosure further includes the examples provided below.

[0096] Polishing experiments were performed using PVD-deposited molybdenum wafers. These blanket wafers were purchased from Advantiv. The film thickness specifications are summarized as follows: Mo: PVD molybdenum.

[0097] Polishing experiment

[0098] In the blanket wafer study, molybdenum blanket wafers and TEOS blanket wafers were polished under baseline conditions. The equipment baseline conditions were: platen speed: 93 rpm, head speed: 87 rpm, membrane pressure: 2.0 psi, and slurry flow rate: 300 ml / min.

[0099] In the following example formulation, the abrasive particle is 1.0 wt % Fuso PL-3C.

[0100] It will be understood that the present disclosure includes many embodiments. These embodiments include but are not limited to the following embodiments.

[0101] Example 1

[0102] This example demonstrates the effectiveness of amino acids in reducing the static etch rate of platinum 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 wt% malonic acid and 1.0 wt% hydrogen peroxide, pH 2.3. The specific amino acids and concentrations used in each composition are listed in Table 1.

[0103] The static etch rate of molybdenum for each of the 16 compositions was evaluated. A 2-inch square coupon wafer having a molybdenum layer was immersed in the corresponding composition (molybdenum side up) at 50° C. for one minute. The molybdenum removal rate was determined by resistivity measurements taken before and after immersion in the composition.

[0104] From the results shown in Table 1, it is clear that the etch rate of molybdenum is lower in the composition with a higher amino acid concentration of 0.5% compared to the composition with a concentration of 0.1%. It is also clear that the etch rate of molybdenum is lower in the composition containing L-histidine, L-lysine, and L-arginine compared to the composition containing glycine, L-valine, and L-serine. The relative Mo RR for polishing 300 mm wafers is shown in Table 1, and the highest Mo RR can be achieved in composition 1B. The compositions 1K and 1O are even higher, and

[0105] Table I

[0106]

[0107]

[0108] Example 2

[0109] This example demonstrates that an alternative oxidant, 0.75 wt% ferric nitrate (instead of hydrogen peroxide) can effectively reduce the static etch rate of molybdenum to less than 0.1% at an elevated temperature of 50°C. At the same time, the Mo RR of the sample wafer polishing can be higher than Sixteen compositions were prepared (Examples 2A, 2B, 2C, 2D, 2E, 2F, 2G, 2H, 2I, 2J, 2K, 2L, 2M, 2N, 2O). Each composition contained 0.08% by weight malonic acid and 1.0% by weight hydrogen peroxide (pH 2.3). The specific amino acids and concentrations used in each composition are listed in Table II.

[0110] Table II

[0111]

[0112]

[0113] Example 3

[0114] This example demonstrates the use of amine compounds with phosphoric acid (i.e., 2-aminoethylphosphonic acid and 3-aminopropylphosphonic acid) and amine compounds with sulfonic acid (i.e., 3-amino-1-propanesulfonic acid and aminomethanesulfonic acid). Nine compositions (Examples 3A, 3B, 3C, 3D, 3E, 3F, 3G, 3H, 3I) were prepared, each containing 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. For compositions with amino-phosphonic acid concentrations above 0.35% and 0.5%, such as Examples 3C and 3E, respectively, the static etch rate of platinum at an elevated temperature of 50°C can be reduced to below 0.08 wt%. The Mo static etch rate for sulfamic acid (Examples 3G and 31) was not as significantly reduced as for aminophosphoric acid, but was still lower than that for control Example 3A, as shown in Table III.

[0115] Table III

[0116]

[0117]

[0118] Example 4

[0119] This example demonstrates the effects of various amino acid combinations (glycine and L-histidine) and oxidants (hydrogen peroxide, potassium iodate, and ferric nitrate) on Mo static etch rates and 300 mm Mo removal rates. Twelve compositions (Examples 4A, 4B, 4C, 4D, 4E, 4F, 4G, 4H, 41, 4J, 4K) were prepared. Each composition contained 0.08 wt% malonic acid and 1.0 wt% hydrogen peroxide at pH 2.3. The specific amino acids, oxidants, and their relative concentrations used in each composition are listed in Table IV. For compositions 4F and 4G with potassium iodate as the oxidant, the Mo static etch rate at 50°C was significantly reduced to below 0.08 wt%. And the Mo removal rate is higher than Compositions 4H and 4J with ferric nitrate as the oxidant have even lower Mo static etch rates, despite having relatively low Mo removal rates, of approximately

[0120] Table IV

[0121]

[0122] Figure 1 The static etch rate of molybdenum at 50°C relative to the molybdenum removal rate is shown for different oxidants: (1) H2O2, (2) Oxidant B: KIO3, and (3) Oxidant C: Fe(NO3)3. Of the three oxidants used in the compositions (1A-4K) of the present disclosure, the H2O2-based formulations generally resulted in higher static etch rates of molybdenum at 50°C. Generally, the KIO3-based formulations resulted in lower static etch rates and higher Mo removal rates than the H2O2-based formulations. Generally, the Fe(NO3)3-based formulations resulted in lower static etch rates than the H2O2-based formulations and higher Mo removal rates than the H2O2-based formulations and the KIO3-based formulations.

[0123] In some embodiments, the RR of Mo is between about 500 and about In some embodiments, the RR of SiN is between about 1 and about In some embodiments, the removal rate selectivity of Mo to SiN is between about 500:1 and about 5:1, more preferably between about 400:1 and about 10:1.

[0124] In some embodiments, the RR of TEOS is between about 50 and about In some embodiments, the removal rate selectivity of Mo to TEOS is between about 1:1 and about 50:1, more preferably between about 1:1 and about 10:1.

[0125] In some embodiments, the chemical mechanical polishing composition does not contain anionic polymers or anionic surfactants.

[0126] In some embodiments, the chemical mechanical polishing composition comprises a cationic surfactant. In the embodiment shown, the cationic surfactant is T-403 (polyetheramine). Jeffamine T-403 (CAS No. 39423-51-3) is characterized by repeating propylene oxide units in the backbone. Jeffamine T-403 is a trifunctional primary amine with an average molecular weight of approximately 440. Its amine group is located on a secondary carbon atom at the end of the aliphatic polyether chain.

[0127] 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, an oxidizing agent;

[0128] The second embodiment may include the first embodiment, wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, ferric nitrate monohydrate, and potassium iodate oxidizing agents, and mixtures thereof.

[0129] In the embodiment shown, the second chemical additive comprises potassium iodate, and the third chemical additive comprises malonic acid.

[0130] A third embodiment can include any of the first and second embodiments, wherein the composition further comprises a carboxylic acid complexed with iron ions as a stabilizer.

[0131] A fourth embodiment may include any one of the first to third embodiments, wherein the amine compound is selected from carboxylic acids, phosphoric acids, and sulfonic acids.

[0132] A fifth embodiment may include any of the first to fourth embodiments, 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. In the embodiment shown, the first chemical additive comprises L-histidine and glycine. In a further embodiment, the first chemical additive is L-histidine, and the second chemical additive is KIO 3 .

[0133] A sixth embodiment may include any one of the first to fifth embodiments, wherein the amine compound is an aminophosphoric acid selected from the group consisting of (aminomethyl)phosphoric acid, (2-aminoethyl)phosphoric acid, and (3-aminoethyl)phosphoric acid, and mixtures thereof.

[0134] A seventh embodiment may include any one of the first to sixth embodiments, wherein the amine compound is an aminosulfonic acid selected from aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 3-amino-1-propanesulfonic acid, and mixtures thereof.

[0135] An eighth embodiment may include any of the first to seventh embodiments, wherein the abrasive particles include cationic or anionic silica, zirconium oxide, and aluminum oxide.

[0136] In a ninth embodiment, a method of chemically mechanically polishing a substrate having a molybdenum layer may comprise, consist of, or consist essentially of: (a) contacting a substrate with any one of the first to eighth polishing composition embodiments; (b) moving the polishing composition relative to the substrate; and (c) grinding the substrate to remove a portion of the molybdenum layer or remove the molybdenum layer from the substrate, thereby polishing the substrate.

[0137] The above embodiments, including the working examples, are exemplary of the numerous embodiments that may be constructed from the present disclosure. It is contemplated that many other configurations of the method may be used, and that the materials used in the method may be selected from a variety of materials other than those specifically disclosed.

Claims

1. A chemical mechanical polishing composition comprising: 0.1 to 20 wt %, preferably 0.1 to 10 wt %, more preferably 0.1 to 5 wt %, most preferably 0.1 to 3 wt % abrasive grains; 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, wherein the first chemical additive comprises an amine compound further comprising a carboxylic acid or a phosphoric acid or a sulfonic acid; 0.01 wt% to 0.2 wt% or preferably 0.01 wt% to 0.05 wt% of a second chemical additive, wherein the second chemical additive is an oxidizing agent selected from hydrogen peroxide, ferric nitrate, potassium iodate, and mixtures thereof; water-miscible solvents; and Optionally biocides; and pH adjusters; The chemical mechanical polishing composition has a pH of 2-7, preferably 2-5, more preferably 2-4, and most preferably 2-3.

5.

2. The chemical mechanical polishing composition of claim 1 , wherein the abrasive particles are selected from the group consisting of 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.

3. The chemical mechanical polishing composition according to 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. The chemical mechanical polishing composition according to claim 1, wherein the amine compound is aminophosphoric acid selected from the group consisting of (aminomethyl)phosphoric acid, (2-aminoethyl)phosphoric acid, (3-aminoethyl)phosphoric acid, and mixtures thereof. 5 . The chemical mechanical polishing composition according to claim 1 , wherein the amine compound is aminosulfonic acid selected from aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 3-amino-1-propanesulfonic acid, and a mixture thereof. The chemical mechanical polishing composition according to claim 1 , wherein the oxidizing agent is ferric nitrate or potassium iodate.

7. The chemical mechanical polishing composition according to claim 1, wherein the static etching rate of molybdenum at 50 degrees Celsius is less than More preferably less than 8. The chemical mechanical polishing composition according to 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 according to claim 1, wherein the chemical mechanical polishing composition comprises a cationic surfactant; or The chemical mechanical polishing composition does not contain anionic polymers or anionic surfactants.

10. A chemical mechanical polishing composition comprising: 0.1 to 10 wt %, preferably 0.1 to 5 wt %, more preferably 0.1 to 3 wt %, most preferably 0.5 to 2 wt % abrasive grains; 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, wherein the first chemical additive comprises an amine compound further comprising a carboxylic acid or a phosphoric acid or a sulfonic acid; 0.01 wt% to 0.0 wt% or preferably 0.01 wt% to 0.5 wt% of a second chemical additive, wherein the second chemical additive is an oxidizing agent selected from ferric nitrate, potassium iodate, and mixtures thereof; water-miscible solvents; and Optionally biocides; and pH adjusters; wherein the chemical mechanical polishing composition has a pH of 2-7, preferably 2-5, more preferably 2-4, most preferably 2-3.5; and The chemical mechanical polishing composition does not contain hydrogen peroxide.

11. The chemical mechanical polishing composition according to 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. The chemical mechanical polishing composition according to claim 10, wherein the amine compound is aminophosphoric acid selected from the group consisting of (aminomethyl)phosphoric acid, (2-aminoethyl)phosphoric acid, (3-aminoethyl)phosphoric acid, and mixtures thereof.

13. The chemical mechanical polishing composition according to claim 10, wherein the amine compound is aminosulfonic acid selected from aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 3-amino-1-propanesulfonic acid and a mixture thereof.

14. The chemical mechanical polishing composition according to 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 according to any one of claims 1 to 14, wherein the static etching rate of molybdenum at 50 degrees Celsius is less than Preferably less than More preferably less than 16. A method of chemically mechanically polishing (CMP) a semiconductor substrate having at least one surface comprising a molybdenum-containing film, comprising: providing the semiconductor substrate; Provide polishing pads; 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 The at least one surface is polished.

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

18. The method according to claim 17, wherein the silicon oxide film is a SiO2 film, and the removal selectivity of molybdenum:silicon oxide is greater than 10, preferably greater than 30, and more preferably greater than 50.

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

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

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