TWI518157B - A slurry composition having tunable dielectric polishing selectivity and method of polishing a substrate - Google Patents

Description

Slurry composition with adjustable dielectric polishing selectivity and method for polishing substrate

The present invention is generally directed to the field of chemical mechanical polishing. In particular, the present invention relates to chemical mechanical polishing slurry compositions and methods of chemical mechanical polishing of semiconductor materials, and more particularly to dielectric films [eg, for high-k metal gates, copper barriers, interlayers). In the dielectric (ILD) and shallow trench isolation (STI) process, the cerium oxide and Si ₃ N ₄ ] of the dielectric layer of the chemical mechanically polished semiconductor structure exhibits a trimpable removal rate and a removal rate selectivity. Chemical mechanical polishing of the slurry composition.

In the fabrication of integrated circuits and other electronic devices, multiple layers of conductors, semiconductors, and dielectric materials are deposited or removed from the surface of the semiconductor wafer. Thin layers of conductors, semiconductors, and dielectric materials can be deposited using a variety of deposition techniques. Common deposition techniques in modern processing include physical vapor deposition (PVD) [known as so-called sputtering], chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), and electroplating. (ECP).

When the layers of materials are successively deposited and removed, the uppermost surface of the wafer becomes non-flat. Since subsequent semiconductor processing (eg, metallization processes) requires a flat surface of the wafer, it is desirable to planarize the wafer. Flattening helps remove undesired surface topography and surface defects such as surface roughness, material agglomeration, lattice damage, scratches, and contaminated layers or materials.

Chemical mechanical planarization, or chemical mechanical polishing (CMP), is a common technique used to planarize substrates, such as semiconductor wafers. In conventional CMP, the wafer is mounted on a carrier assembly and placed in contact with the polishing pad in the CMP apparatus. The carrier assembly provides controlled pressure to the wafer against the polishing pad. The polishing pad is moved (eg, rotated) relative to the wafer using an external driving force. At the same time, a polishing composition ("slurry") or other slurry is provided between the wafer and the polishing pad. In this way, the surface of the wafer is polished by the chemical and mechanical action of the surface of the polishing pad and the slurry to planarize it.

A method for isolating components of a semiconductor device, referred to as a shallow trench isolation (STI) process, is conventionally used in a layer of tantalum nitride (Si ₃ N ₄ ) formed on a germanium substrate, in which the tantalum nitride layer is The shallow trenches are formed and a dielectric material (eg, an oxide) is deposited to fill the trenches. Excess dielectric material is typically deposited over the substrate to ensure complete filling of the trench. The excess dielectric material layer is then removed using a chemical mechanical planarization technique to expose the tantalum nitride layer.

Previous device designs have emphasized the chemical mechanical planarization selectivity of yttrium oxide for tantalum nitride (i.e., higher yttrium oxide removal rate relative to tantalum nitride removal rate). In their device design, the tantalum nitride layer is used as a chemical mechanical planarization process stop layer.

Recently, specific device designs have required polishing compositions for chemical mechanical planarization processes to provide cerium oxide selectivity over polysilicon (i.e., higher cerium oxide removal rates relative to polysilicon removal rates).

A polishing formulation for the chemical mechanical planarization process that provides for the selectivity of at least one of cerium oxide and tantalum nitride relative to polycrystalline germanium is disclosed in U.S. Patent Application Publication No. 2007/0077865 to Dysard et al. Dysard et al. disclose a method of chemically mechanically polishing a substrate, the method comprising: (i) contacting a substrate comprising polycrystalline germanium and a material selected from the group consisting of cerium oxide and tantalum nitride with a chemical mechanical polishing system comprising: (a) An abrasive, (b) a liquid carrier, (c) from about 1 ppm to about 100 ppm of a polyepoxide having an HLB of about 15 or less, based on the weight of the liquid carrier and any component dissolved or suspended therein. An ethane/propylene oxide copolymer, and (d) a polishing pad; (ii) moving the polishing pad relative to the substrate; and (iii) polishing the substrate to abrade at least a portion of the substrate.

Another type of polishing formulation for a chemical mechanical planarization process that provides for the selectivity of at least one of cerium oxide and tantalum nitride relative to polysilicon is disclosed in U.S. Patent No. 6,626,968 to Park et al. Park et al. disclose a chemical mechanical polishing composition for simultaneously grinding a pH 7 to 11 having a surface of a cerium oxide layer and a polycrystalline germanium layer in the form of a slurry, the slurry composition consisting essentially of: water; selected from the group consisting of dioxide An abrasive particle of cerium (SiO ₂ ), alumina (Al ₂ O ₃ ), cerium oxide (CeO ₂ ), manganese oxide (Mn ₂ O ₃ ), a mixture thereof, and from about 0.001 to about 5 weight percent Free choice of polyvinyl methyl ether (PVME), polyethylene glycol (PEG), polyoxyethylene 23 dodecyl ether (POLE), polypropionic acid (PPA), polyacrylic acid (PAA), polyether glycol diether (PEGBE), a polymeric additive of the group formed by the mixture thereof; wherein the polymeric additive enhances the selectivity ratio of the ruthenium oxide removal layer relative to the removal of the polycrystalline germanium layer.

Nonetheless, to support the dynamics of device design for semiconductor system fabrication, there is a continuing need for chemical mechanical polishing compositions that are formulated to provide a balance of abrasive properties that meets the changing design requirements to accommodate changing design needs. For example, for showing a dielectric film (e.g. silicon oxide and Si ₃ N ₄₎ can be trimmed of (tailorable) removal rate and the removal rate selectivity of a chemical mechanical polishing composition is still in demand.

The present invention provides a chemical mechanical polishing slurry composition comprising the following initial components: water; an abrasive; a halogenated quaternary ammonium compound according to formula (I):

Wherein R ⁸ is selected from the group consisting of C _1-10 alkyl and C _1-10 hydroxyalkyl, and X ¹ is selected from the group consisting of chlorides, bromides, halides of iodides and fluorides, R ⁹ , R ¹⁰ and R ¹¹ Each is independently selected from saturated or unsaturated C _1-10 alkyl, C _1-10 haloalkyl, C _6-15 aryl, C _6-15 haloaryl, C _6-15 aralkyl and C _{6- 15} haloaralkyl, and the anion of formula (I) is any anion that balances the cation + charge in formula (I); and, if desired, a diquaternary material according to formula (II):

Wherein each A is independently selected from N and P, and R ¹ is selected from the group consisting of saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl and C ₆ -C ₁₅ aralkyl, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently selected from hydrogen, saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl, C ₆ -C ₁₅ aralkyl and C _6- C ₁₅ alkaryl, and the anion in formula (II) is any combination of anions or anions that balance the charge of cation 2+ in formula (II).

The present invention provides a chemical mechanical polishing slurry composition comprising the following initial components: water; 0.1 to 40% by weight of an abrasive; 0.001 to 1% by weight of a halogenated quaternary ammonium compound according to formula (I), wherein R ⁸ is It is selected from C _1-10 alkyl and C _1-10 hydroxyalkyl, X ¹ is selected from the group consisting of chloride, bromide, iodide and fluoride halide, and R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from Saturated or unsaturated C _1-10 alkyl, C _1-10 haloalkyl, C _6-15 aryl, C _6-15 haloaryl, C _6-15 aralkyl and C _{6-15 haloaralkyl} And the anion in the formula (I) is any anion of the cation + charge in the equilibrium formula (I); and, 0 to 1 wt% of the double quaternary substance according to formula (II), wherein each A is independently selected from N and P, R ¹ is selected from the group consisting of saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl and C ₆ -C ₁₅ aralkyl, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ And R ⁷ are each independently selected from hydrogen, saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl, C ₆ -C ₁₅ aralkyl and C ₆ -C ₁₅ alkaryl, and The anion in (II) is any combination of anions or anions of the cation 2+ charge in equilibrium (II).

The present invention provides a chemical mechanical polishing slurry composition comprising the following initial components: water; 0.1 to 10% by weight of an abrasive; 0.002 to 0.5% by weight of a halogenated quaternary ammonium compound according to formula (I), wherein R ⁸ It is selected from the group consisting of a -(CH ₂ ) ₂ - group, a -CH ₂ CHOH group, a -(CH ₂ ) ₈ - group and -(CH ₂ ) ₂ -CHOH, and the X ¹ group is selected from the group consisting of chloride and bromide. a halide, R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from the group consisting of a —CH ₃ group and a —CH ₂ CH ₃ group, and the anion in the formula (I) is selected from the group consisting of a chloride anion and a bromide anion; , 0.002 to 0.2 wt% of a double quaternary substance according to formula (II), wherein each A is N, R ¹ is a -(CH ₂ ) ₄ - group, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} each a -(CH ₂ ) ₃ CH ₃ group.

The present invention provides a chemical mechanical polishing slurry composition comprising the following initial components: water; 0.1 to 10% by weight of an abrasive, wherein the abrasive is a colloidal ceria abrasive having an average particle size of 20 to 50 nm; 0.01 to 0.2 Wt% is a halogenated quaternary ammonium compound according to formula (I) wherein R ⁸ is selected from the group consisting of a -(CH ₂ ) ₂ - group, a -CH ₂ CHOH group, a -(CH ₂ ) ₈ - group -(CH ₂ ) ₂ -CHOH, X ¹ is selected from the halides of chloride and bromide, and R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from the group consisting of a -CH ₃ group and a -CH ₂ CH ₃ group, And the anion in the formula (I) is selected from the group consisting of a chloride anion and a bromide anion; and, 0.01 to 0.05 wt% of a double quaternary substance according to formula (II), wherein each A is N and R ¹ is -(CH) _{2) 4} - ^{group, R 2, R 3, R} 4, R 5, R 6 and R ⁷ are each - (CH _{2) 3} CH ₃ group, and balanced formula (II) in the cationic charge of anion 2+ It is selected from the group consisting of a halide anion and a hydroxide anion.

The present invention provides a method of making a chemical mechanical polishing slurry composition, the method comprising: providing water; providing an abrasive; providing a halogenated quaternary ammonium compound according to formula (I), wherein R ⁸ is selected from C _1-10 An alkyl group and a C _1-10 hydroxyalkyl group, X ¹ is selected from the group consisting of chlorides, bromides, iodides and fluoride halides, and R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from saturated or unsaturated C _{1 . -10} alkyl, C _1-10 haloalkyl, C _6-15 aryl, C _6-15 haloaryl, C _6-15 aralkyl and C _{6-15 haloaralkyl} , and formula (I) The anion in the equilibrium is any anion of the cation + charge in the equilibrium formula (I); and, if necessary, a double quaternary substance according to formula (II), wherein each A is independently selected from N and P, and the R ¹ is selected Self-saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl and C ₆ -C ₁₅ aralkyl, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently Selected from hydrogen, saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl, C ₆ -C ₁₅ aralkyl and C ₆ -C ₁₅ alkaryl, and an anion of formula (II) To balance any anion or anion of the cation 2+ charge in formula (II); provide a pH adjuster; An abrasive, a halogenated quaternary ammonium compound according to formula (I), and optionally a double quaternary substance according to formula (II) to form a chemical mechanical polishing slurry composition; and, if necessary, a pH adjusting agent To the slurry to adjust the pH of the chemical mechanical polishing slurry composition to <7.

The present invention provides a method of chemically mechanically polishing a substrate, the method comprising: providing a substrate, wherein the substrate comprises at least one of cerium oxide and Si ₃ N ₄ ; providing a chemical mechanical polishing slurry composition according to claim 1 of the scope of the patent application, Wherein the concentration of the halogenated quaternary ammonium compound according to formula (I) and the concentration of the double quaternary material according to formula (II) are selected to tailor the chemical mechanical polishing slurry composition to cerium oxide and Si ₃ N ₄ at least one of which exhibits a removal rate; providing a chemical mechanical polishing pad having an abrasive surface; generating a dynamic contact at an interface between the polishing surface of the chemical mechanical polishing pad and the substrate at a downward pressure of 0.69 to 34.5 kPa; and, dispensing chemistry Mechanically grinding the slurry composition to the interface or interface between the chemical mechanical polishing pad of the chemical mechanical polishing pad and the substrate; wherein the chemical mechanical polishing slurry composition provided has a pH of <7; wherein the substrate is ground; and wherein Some of the at least one of the Si ₃ N ₄ is removed from the substrate.

The selection of the specific formulation of the chemical mechanical polishing slurry composition of the present invention used in the chemical mechanical polishing method of the present invention is the key to providing a target removal rate of at least one of cerium oxide, Si ₃ N ₄ and polycrystalline germanium; preferably cerium oxide is provided. The target removal rate selectivity between at least two of Si ₃ N ₄ and polycrystalline germanium (more preferably between cerium oxide and Si ₃ N ₄ ).

A substrate suitable for the chemical mechanical polishing method of the present invention comprises a semiconductor substrate on which at least one of yttrium oxide, Si ₃ N ₄ and polysilicon is deposited. Preferably, the substrate used comprises at least one of cerium oxide and Si ₃ N ₄ . More preferably, the substrate used is deposited with yttrium oxide on at least one of SiC, SiCN, Si ₃ N ₄ , SiCO and polycrystalline germanium (preferably Si ₃ N ₄ ).

Abrasives suitable for use in the chemical mechanical polishing slurry composition of the present invention include, for example, inorganic oxides, inorganic hydroxides, inorganic hydroxide oxides, metal borides, metal carbides, metal nitrides, polymer particles, and the like. a mixture of at least one of the foregoing. Suitable inorganic oxides include, for example, cerium oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), cerium oxide (CeO ₂ ), manganese oxide (MnO ₂ ), titanium oxide (TiO). ₂ ) or a combination comprising at least one of the foregoing oxides. If desired, modified forms of these inorganic oxides may also be used, for example, inorganic oxide particles coated with an organic polymer and inorganic coated particles. Suitable metal carbides, borides, and nitrides include, for example, tantalum carbide, tantalum nitride, tantalum carbonitride (SiCN), boron carbide, tungsten carbide, zirconium carbide, aluminum boride, tantalum carbide, titanium carbide, or A combination of at least one of the foregoing metal carbides, borides, and nitrides. Preferably, the abrasive is a colloidal ceria abrasive.

The abrasive used in the chemical mechanical polishing slurry composition of the present invention preferably has an average particle size of from 5 to 200 nm, more preferably from 20 to 100 nm, still more preferably from 20 to 60 nm, most preferably from 20 to 50 nm.

The chemical mechanical polishing slurry composition of the present invention preferably contains 0.1 to 40% by weight, more preferably 0.1 to 20% by weight, still more preferably 1 to 20% by weight, most preferably 1 to 10% by weight of the abrasive.

The chemical mechanical polishing slurry composition of the present invention preferably comprises a colloidal ceria abrasive having an average particle size of 20 to 100 nm. Still more preferably, the chemical mechanical polishing slurry composition of the present invention comprises from 1 to 10% by weight of a colloidal ceria abrasive having an average particle size of from 20 to 60 nm. Most preferably, the chemical mechanical polishing slurry composition of the present invention comprises from 1 to 10% by weight of a colloidal ceria abrasive having an average particle size of from 20 to 50 nm.

The water contained in the chemical mechanical polishing slurry composition of the present invention is preferably at least one of deionized water and distilled water to limit sporadic impurities.

The chemical mechanical polishing slurry composition of the present invention comprises a halogenated quaternary ammonium compound according to formula (I) as an initial component:

Wherein R ⁸ is selected from the group consisting of C _1-10 alkyl and C _1-10 hydroxyalkyl (preferably R ⁸ is selected from C _1-5 alkyl and C _1-5 hydroxyalkyl, more preferably R ⁸ It is selected from a C _1-4 alkyl group and a C _1-4 hydroxyalkyl group, and most preferably the R ⁸ group is selected from the group consisting of a -(CH ₂ ) ₂ - group, a -CH ₂ CHOH group, -(CH ₂ ) ₃ - a group and -(CH ₂ ) ₂ -CHOH]; X ¹ is selected from the group consisting of chlorides, bromides, iodides and fluoride halides (preferably X ¹ is selected from the group consisting of chlorides, bromides and iodides, Most preferably X ¹ is selected from the group consisting of chloride and bromide; R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from saturated or unsaturated C _1-10 alkyl, C _1-10 haloalkyl, C _{6- 15} aryl, C _6-15 haloaryl, C _6-15 aralkyl and C _{6-15 haloaralkyl} (preferably R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from C _1-5 alkane And a C _1-5 haloalkyl group, more preferably R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from C _1-4 alkyl groups, most preferably R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from - a CH ₃ group and a -CH ₂ CH ₃ group); and, the anion in the formula (I) is any anion which balances the cation + charge in the formula (I) (preferably the anion in the formula (I) is selected from Halide anion, hydroxide anion and nitrite anion, more It is a halide anion and hydroxide anion, most preferably an anion selected from chloride and bromide anions halide anion). Preferably, the chemical mechanical polishing slurry composition of the present invention comprises 0.001 to 1% by weight (more preferably 0.002 to 0.5% by weight, still more preferably 0.005 to 0.2% by weight, most preferably 0.01 to 0.2% by weight) as an initial component. A halogenated quaternary ammonium compound according to formula (I). Most preferably, the chemical mechanical polishing slurry composition of the present invention comprises 0.01 to 0.2% by weight of an initial component selected from (2-bromoethyl)trimethylammonium bromide, (2-chloroethyl)trimethylammonium chloride, (3) -bromopropyl)trimethylammonium bromide, (3-chloroethyl)trimethylammonium chloride, (3-bromopropyl)triethylammonium bromide and (3-chloro-2-hydroxypropyl)trimethylammonium chloride A halogenated quaternary ammonium compound according to formula (I). The incorporation of a halogenated quaternary ammonium compound according to formula (I) increases the removal rate of polycrystalline germanium, cerium oxide and Si ₃ N ₄ under the grinding conditions described in the examples; and for cerium oxide and Si ₃ N ₄ The removal rate has an adjustable selectivity.

The chemical mechanical polishing slurry composition of the present invention optionally contains a double quaternary substance according to formula (II) as an initial component:

Wherein each A is independently selected from N and P, preferably each A is N; and R ¹ is selected from the group consisting of saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl and C ₆ -C ₁₅ An aralkyl group (preferably a C ₂ -C ₁₀ alkyl group, more preferably a C ₂ -C ₆ alkyl group, still more preferably a -(CH ₂ ) ₆ - group and a -(CH ₂ ) ₄ - group, Most preferably -(CH ₂ ) ₄ -group]; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently selected from hydrogen, saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl, C ₆ -C ₁₅ aralkyl and C ₆ -C ₁₅ alkaryl (preferably hydrogen and C ₁ -C ₆ alkyl, more preferably hydrogen and butyl, most preferably And the anion in the formula (II) is a combination of any anion or anion of the cation 2+ charge in the equilibrium formula (II). Preferably, the anion in the formula (II) is selected from the group consisting of a halide anion and hydrogen. An oxyanion anion, a nitrate anion, a sulfate anion and a phosphate anion, more preferably a halide anion and a hydroxide anion, most preferably a hydroxide anion]. The chemical mechanical polishing composition of the present invention optionally contains 0 to 1% by weight (preferably 0 to 0.5% by weight, more preferably 0.001 to 0.5% by weight, still more preferably 0.002 to 0.2% by weight, still more preferably 0.005). Up to 0.1% by weight, preferably 0.01 to 0.05% by weight, based on the double quaternary substance of the formula (II) which is an initial component. Most preferably, the chemical mechanical polishing composition of the present invention comprises 0.01 to 0.05% by weight of a double quaternary substance according to formula (II), wherein each A is N; and R ¹ is -(CH ₂ ) ₄ - And R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} each a —(CH ₂ ) ₃ CH ₃ group. Under the grinding conditions described in the examples, the incorporation of a dual quaternary material according to formula (II) in the chemical mechanical polishing slurry composition of the present invention provides increased cerium oxide removal rate, reduced Si ₃ N ₄ removal rate and reduced polysilicon removal rate.

The chemical mechanical polishing slurry composition of the present invention further contains, if necessary, an additional additive selected from the group consisting of a dispersing agent, a surfactant, a buffering agent and a biocide.

The chemical mechanical polishing slurry composition of the present invention provides efficacy in the pH range of 2 to <7. Preferably, the chemical mechanical abrasive slurry composition used provides efficacy in the pH range of 2 to 5. Most preferably, the chemical mechanical abrasive slurry composition used provides efficacy in the pH range of 2 to 4. Acids suitable for adjusting the pH of the chemical mechanical polishing slurry composition include, for example, phosphoric acid, nitric acid, sulfuric acid, and hydrochloric acid. Acids suitable for adjusting the pH of the chemical mechanical polishing slurry composition include, for example, ammonium hydroxide and potassium hydroxide.

Preferably, the chemical mechanical polishing slurry composition of the present invention exhibits 200 to 3,000 under the measurement of the grinding conditions described in the examples. /min (preferably 300 to 2,100 /min) The repairable cerium oxide removal rate.

Preferably, the chemical mechanical polishing slurry composition of the present invention exhibits 300 to 2,000 under the measurement of the grinding conditions described in the examples. /min (preferably 300 to 1,000 /min) The repairable Si ₃ N ₄ removal rate.

Preferably, the chemical mechanical polishing slurry composition of the present invention exhibits a cerium oxide to Si ₃ N ratio of 1:2 to 10:1 (more preferably 1:2 to 7:1) as measured by the grinding conditions described in the examples. ₄ can be trimmed to remove selectivity selectivity.

Preferably, the chemical mechanical polishing slurry composition of the present invention comprises the following initial components: water; 0.1 to 40% by weight (preferably 0.1 to 20% by weight, still more preferably 1 to 20% by weight, most preferably 1 to 10% by weight) %) an abrasive having an average particle size of 5 to 200 nm (preferably 20 to 100 nm, more preferably 20 to 60 nm, most preferably 20 to 50 nm); 0.001 to 1 wt% (more preferably 0.002 to 0.5 wt%, still more Preferably, it is from 0.005 to 0.2% by weight, most preferably from 0.01 to 0.2% by weight, based on the halogenated quaternary ammonium compound of formula (I), wherein R ⁸ is selected from the group consisting of C _1-10 alkyl and C _1-10 hydroxy Alkyl group [preferably R ⁸ is selected from C _1-5 alkyl and C _1-5 hydroxyalkyl, more preferably R ⁸ is selected from C _1-4 alkyl and C _1-4 hydroxyalkyl, most Preferably, R ⁸ is selected from the group consisting of -(CH ₂ ) ₂ -, -CH ₂ CHOH, -(CH ₂ ) ₈ - and -(CH ₂ ) ₂ -CHOH]; X ¹ is selected from chlorine a halide of a compound, a bromide, an iodide and a fluoride (preferably X ¹ is selected from the group consisting of chloride, bromide and iodide, preferably X ¹ is selected from the group consisting of chloride and bromide); R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from saturated or unsaturated C _1-10 alkyl, C _1-10 haloalkyl, C _6-15 aryl, C _6-15 haloaryl, C _6-15 aralkyl With C _{6-15 haloaralkyl} (preferably R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from C _1-5 alkyl and C _1-5 haloalkyl, more preferably R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from C _{1 a -4} alkyl group, most preferably R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from a -CH ₃ group and a -CH ₂ CH ₃ group); and, the anion in the formula (I) is a balanced formula (I) Any anion of a cation + charge (preferably the anion in formula (I) is selected from the group consisting of a halide anion, a hydroxide anion and a nitrite anion, more preferably a halide anion and a hydroxide anion, preferably Is a halide anion selected from the group consisting of chloride anions and bromide anions; 0 to 1 wt% (preferably 0 to 0.5 wt%, more preferably 0.001 to 0.5 wt%, still more preferably 0.002 to 0.2 wt%) Still more preferably 0.005 to 0.1 wt%, most preferably 0.01 to 0.05 wt%) according to the double quaternary substance of formula (II), wherein each A is independently selected from N and P, preferably each A is N; R ¹ is selected from the group consisting of saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl and C ₆ -C ₁₅ aralkyl (preferably C ₂ -C ₁₀ alkyl, more preferably C ₂ a -C ₆ alkyl group, more preferably a -(CH ₂ ) ₆ - group and a -(CH ₂ ) ₄ - group, most preferably a -(CH ₂ ) ₄ - group]; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently selected from hydrogen, saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl, C ₆ -C ₁₅ aralkyl And C ₆ -C ₁₅ alkaryl (preferably hydrogen and C ₁ -C ₆ alkyl, more preferably hydrogen and butyl, most preferably butyl); and, the anion in formula (II) is balanced (II) a combination of any anion or anion of a cationic 2+ charge [preferably the anion of the formula (II) is selected from the group consisting of a halide anion, a hydroxide anion, a nitrate anion, a sulfate anion and a phosphoric acid The root anion is more preferably a halide anion and a hydroxide anion, most preferably a hydroxide anion].

The chemical mechanical polishing method of the present invention comprises: providing a substrate, wherein the substrate comprises at least one of cerium oxide and Si ₃ N ₄ ; providing a chemical mechanical polishing slurry composition according to the present invention, wherein the chemical mechanical polishing slurry composition comprises the following initial Ingredient: water; 0.1 to 40% by weight (preferably 0.1 to 20% by weight, most preferably 1 to 10% by weight) of an abrasive having an average particle size of 5 to 200 nm (preferably 20 to 60 nm, preferably 20 to 50 nm); 0.001 to 1 wt% (more preferably 0.002 to 0.5 wt%, still more preferably 0.005 to 0.2 wt%, most preferably 0.01 to 0.2 wt%) of a halogenated quaternary ammonium compound according to formula (I), wherein R ⁸ is selected from the group consisting of C _1-10 alkyl and C _1-10 hydroxyalkyl (preferably R ⁸ is selected from C _1-5 alkyl and C _1-5 hydroxyalkyl, more preferably R ⁸ is selected from C _1-4 alkyl and C _1-4 hydroxyalkyl, most preferably R ⁸ is selected from the group consisting of -(CH ₂ ) ₂ -, -CH ₂ CHOH, -(CH ₂ ) ₃ - -(CH ₂ ) ₂ -CHOH]; X ¹ is selected from the group consisting of chlorides, bromides, iodides and fluoride halides (preferably X ¹ is selected from the group consisting of chlorides, bromides and iodides, preferably X ¹ is selected from the group consisting of chloride and bromide; R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from saturation or Unsaturated C _1-10 alkyl, C _1-10 haloalkyl, C _6-15 aryl, C _6-15 haloaryl, C _6-15 aralkyl and C _{6-15 haloaralkyl} (compared Preferably, R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from C _1-5 alkyl and C _1-5 haloalkyl, more preferably R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from C _1-4 An alkyl group, most preferably R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from a -CH ₃ group and a -CH ₂ CH ₃ group; and, the anion in formula (I) is in equilibrium (I) Any anion of a cation + charge [preferably the anion in the formula (I) is selected from the group consisting of a halide anion, a hydroxide anion and a nitrite anion, more preferably a halide anion and a hydroxide anion, preferably selected a halide anion from a chloride anion to a bromide anion]; 0 to 1 wt% (preferably 0 to 0.5 wt%, more preferably 0.001 to 0.5 wt%, still more preferably 0.002 to 0.2 wt%, still more Preferably, it is from 0.005 to 0.1% by weight, most preferably from 0.01 to 0.05% by weight, based on the double quaternary substance of formula (II), wherein each A is independently selected from N and P, preferably each A is N; R ¹ Is selected from a saturated or unsaturated C ₁ -C ₁₅ alkyl group, a C ₆ -C ₁₅ aryl group and a C ₆ -C ₁₅ aralkyl group (preferably a C ₂ -C ₁₀ alkyl group, more preferably C ₂ -C ₆ alkyl, more preferably -(CH ₂ ) ₆ - group and -(CH ₂ ) ₄ - group, most preferably -(CH ₂ ) ₄ - group]; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently selected from hydrogen, saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl, C ₆ -C ₁₅ aralkyl and C _6- C ₁₅ alkaryl (preferably hydrogen and C ₁ -C ₆ alkyl, more preferably hydrogen and butyl, most preferably butyl); and, the anion of formula (II) is balanced (II Any combination of anions or anions of a cationic 2+ charge [preferably the anion of formula (II) is selected from the group consisting of halide anions, hydroxide anions, nitrate anions, sulfate anions and phosphate anions) More preferably, it is a halide anion and a hydroxide anion, most preferably a hydroxide anion]; wherein the concentration of the halogenated quaternary ammonium compound according to formula (I) is as desired according to formula (II) The concentration of the grade material is selected to modify the removal rate of the chemical mechanical polishing slurry composition for at least one of cerium oxide and Si ₃ N ₄ ; providing a chemical mechanical polishing pad having an abrasive surface; to 0.69 to 34.5 kPa (0.1 Up to 5 psi), preferably 0.69 to 20.7k The downward pressure of Pa (0.1 to 3 psi) creates dynamic contact at the interface between the polishing surface of the chemical mechanical polishing pad and the substrate; and the interface between the chemical mechanical polishing slurry composition and the chemical mechanical polishing pad of the chemical mechanical polishing pad and the substrate Or in the vicinity of the interface; wherein the chemical mechanical polishing slurry composition provided has a pH of <7 (preferably 2 to <7, more preferably 2 to 5, most preferably 2 to 4); wherein the substrate is ground; Some of the germanium and at least one of the Si ₃ N ₄ are removed from the substrate.

Preferably, the chemical mechanical polishing method of the present invention comprises: providing a substrate, wherein the substrate comprises at least one of cerium oxide and Si ₃ N ₄ ; providing water; and providing a chemical mechanical polishing slurry composition comprising the following initial components: 0.1 To 10 wt% of abrasive, wherein the abrasive is a colloidal ceria abrasive having an average particle size of 20 to 50 nm; 0.01 to 0.2 wt% of a halogenated quaternary ammonium compound according to formula (I), wherein R ⁸ It is selected from the group consisting of a -(CH ₂ ) ₂ - group, a -CH ₂ CHOH group, a -(CH ₂ ) ₃ - group and -(CH ₂ ) ₂ -CHOH, and the X ¹ system is selected from the group consisting of chloride and bromide. a halide, R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from the group consisting of a —CH ₃ group and a —CH ₂ CH ₃ group, and the anion in the formula (I) is selected from the group consisting of a chloride anion and a bromide anion; , 0 to 0.05 wt% of a double quaternary substance according to formula (II), wherein each A is N, R ¹ is a -(CH ₂ ) ₄ - group, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} each a -(CH ₂ ) ₃ CH ₃ group; providing a chemical mechanical polishing pad having an abrasive surface; at 0.69 to 34.5 kPa (0.1 to 5 psi), preferably 0.69 to 20.7 kPa (0.1 to 3 psi) ) downward pressure on the grinding of chemical mechanical polishing pads Dynamically contacting the interface with the substrate; and dispensing the chemical mechanical polishing slurry composition to the interface or interface between the chemical mechanical polishing pad and the substrate of the chemical mechanical polishing pad; wherein the chemical mechanical polishing slurry composition provided has <7 ( Preferably, the pH is from 2 to < 7, more preferably from 2 to 5, most preferably from 2 to 4; wherein the substrate is ground; and some of the at least one of yttrium oxide and Si ₃ N ₄ is removed from the substrate.

Several specific examples of the invention are described in detail in the following examples.

Comparative Example C1 and Examples A1 to A6 Preparation of chemical mechanical polishing slurry composition

The chemical mechanical polishing slurry compositions used in the polishing comparative example PC1 and the polishing examples PA1 to PA6 (i.e., the chemical mechanical polishing slurry compositions C1 and A1 to A6, respectively) were the amounts listed in Table 1, and the components were The balance of deionized water was combined and prepared by adjusting the pH of the composition to the final pH listed in Table 1.

Abrasives I ^* - manufacture of the ^{AZ Electronic Materials Klebosol TM II 1598-} B25 slurry, available from The Dow Chemical Company.

Abrasives II ^£ - Klebosol of manufacture of AZ Electronic Materials ^TM II 30H50i slurry, available from The Dow Chemical Company.

(3-chloro-2-hydroxypropyl) trimethylammonium chloride ^¥, available from Sigma-Aldrich, Inc ..

HBBAH ^€ : N,N,N,N',N',N'-hexabutyl-1,4-butanediamine dihydrate, available from Sachem, Inc.:

Comparative Example PC1 and Examples PA1 to PA6 Chemical mechanical polishing removal rate experiment

The cerium oxide, Si ₃ N ₄ , and polycrystalline germanium removal rate grinding tests were carried out using the chemical mechanical polishing slurry compositions prepared according to Comparative Example C1 and Examples A1 to A6. Specifically, as shown in Table 1, the removal rates of cerium oxide, Si ₃ N ₄ and polysilicon of each of the chemical mechanical polishing slurry compositions of C1 and A1 to A6. A grinding removal rate experiment was performed on a gossip felt wafer. Example PC1 system using Strasbaugh nSpire ^TM CMP model 6EC rotary type polishing platform; Example PA1 to PA6 using Applied Materials Grinder. All milling experiments using IC1010 ^TM polyurethane-polishing pad (from Rohm and Haas Electronic Materials CMP Inc. commercially available) for the downward pressure of 20.7kPa (3 psi), a chemical mechanical polishing slurry composition flow rate of 200ml /min, platform rotation speed 93 rpm and carrier rotation speed 87 rpm. The removal rate was measured before and after the grinding by measuring the film thickness using a KLA-Tencor FX200 measuring tool; the removal rate experimental results are provided in Table 2.

Claims (11)

A chemical mechanical polishing slurry composition comprising the following initial components: water; an abrasive, wherein the abrasive is a colloidal ceria abrasive; and a halogenated quaternary ammonium compound according to formula (I): Wherein R ⁸ is selected from the group consisting of C _1-10 alkyl and C _1-10 hydroxyalkyl, and X ¹ is selected from the group consisting of chlorides, bromides, halides of iodides and fluorides, R ⁹ , R ¹⁰ and R ¹¹ Each is independently selected from saturated or unsaturated C _1-10 alkyl, C _1-10 haloalkyl, C _6-15 aryl, C _6-15 haloaryl, C _6-15 aralkyl and C _{6- 15} haloaralkyl, and the anion of formula (I) is any anion which balances the cation + charge in formula (I); wherein the chemical mechanical polishing slurry composition has a pH of from 2 to < 7 when used. The chemical mechanical polishing slurry composition according to claim 1, wherein the chemical mechanical polishing slurry composition comprises the following initial component: a diquaternary substance according to formula (II): Wherein each A is independently selected from N and P, and R ¹ is selected from the group consisting of saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl and C ₆ -C ₁₅ aralkyl, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently selected from hydrogen, saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl, C ₆ -C ₁₅ aralkyl and C _{a 6-} C ₁₅ alkaryl group, and the anion in the formula (II) is a combination of any anion or anion which balances the charge of the cation 2+ in the formula (II); and/or a pH adjuster selected from the group consisting of phosphoric acid and nitric acid , sulfuric acid, hydrochloric acid, ammonium hydroxide and potassium hydroxide. The chemical mechanical polishing slurry composition according to claim 2, wherein the chemical mechanical polishing slurry composition comprises the following initial components: water; 0.1 to 40% by weight of the colloidal ceria abrasive; 0.001 to 1 wt% a halogenated quaternary ammonium compound according to formula (I); 0 to 1% by weight of the double quaternary material according to formula (II); and a pH adjusting agent selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, and hydroxide Ammonium and potassium hydroxide. The chemical mechanical polishing slurry composition according to claim 2, wherein the chemical mechanical polishing slurry composition comprises the following initial components: water; 0.1 to 10% by weight of the colloidal ceria abrasive; 0.002 to 0.5 wt. % according to the halogenated quaternary ammonium compound of formula (I) wherein R ⁸ is selected from the group consisting of a -(CH ₂ ) ₂ - group, a -CH ₂ CHOH group, a -(CH ₂ ) ₃ - group -(CH ₂ ) ₂ -CHOH, X ¹ is selected from the halides of chloride and bromide, and R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from the group consisting of a -CH ₃ group and a -CH ₂ CH ₃ group, And the anion in the formula (I) is selected from the group consisting of a chloride anion and a bromide anion; 0.002 to 0.2 wt% of the double quaternary substance according to formula (II), wherein each A is N and R ¹ is -(CH) _{2) 4} - group, and ^{R 2, R 3, R 4} , R 5, R 6 and R ⁷ are each - (CH _{2) 3} CH ₃ group; and a pH adjusting agent selected from phosphoric acid, nitric acid , sulfuric acid, hydrochloric acid, ammonium hydroxide and potassium hydroxide. The chemical mechanical polishing slurry composition according to claim 2, wherein the chemical mechanical polishing slurry composition comprises the following initial components: water; 0.1 to 10% by weight of the colloidal ceria abrasive, wherein the colloidal state The cerium oxide abrasive has an average particle size of 20 to 50 nm; 0.01 to 0.2% by weight of the halogenated quaternary ammonium compound according to formula (I), wherein R ⁸ is selected from the group consisting of -(CH ₂ ) ₂ -, CH ₂ CHOH group, -(CH ₂ ) ₃ - group and -(CH ₂ ) ₂ -CHOH, X ¹ is selected from chloride and bromide halides, and R ⁹ , R ¹⁰ and R ¹¹ are each independently Selected from a -CH ₃ group and a -CH ₂ CH ₃ group, and the anion in the formula (I) is selected from a chloride anion and a bromide anion; 0.01 to 0.05 wt% of the double four according to formula (II) a material of the formula wherein each A is N, R ¹ is a -(CH ₂ ) ₄ - group, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} each -(CH ₂ ) ₃ CH ₃ a group, and an anion which balances the charge of the cation 2+ in the formula (II) is selected from the group consisting of a halide anion and a hydroxide anion; and a pH adjuster selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, ammonium hydroxide and Potassium hydroxide. A method of chemically polishing a substrate, the method comprising: providing a substrate, wherein the substrate comprises at least one of cerium oxide and Si ₃ N ₄ ; and the chemical mechanical polishing slurry composition according to claim 1 of the patent application, wherein The concentration of the halogenated quaternary ammonium compound according to formula (I) is selected to modify the removal rate exhibited by the chemical mechanical polishing slurry composition for at least one of cerium oxide and Si ₃ N ₄ ; a chemical mechanical polishing pad; a dynamic contact at an interface between the polishing surface of the chemical mechanical polishing pad and the substrate at a downward pressure of 0.69 to 34.5 kPa; and dispensing the chemical mechanical polishing slurry composition to the chemical mechanical polishing pad The chemical mechanical polishing slurry composition has a pH of <7; wherein the substrate is ground; and wherein the cerium oxide and Si ₃ N _{4 are} Some of at least one of the ones are removed from the substrate. The method of claim 6, wherein the chemical mechanical polishing slurry composition comprises the following initial components: a diquaternary substance according to formula (II): Wherein each A is independently selected from N and P, and R ¹ is selected from the group consisting of saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl and C ₆ -C ₁₅ aralkyl, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently selected from hydrogen, saturated or unsaturated C ₁ -C ₁₅ alkyl, C ₆ -C ₁₅ aryl, C ₆ -C ₁₅ aralkyl and C _{a 6-} C ₁₅ alkaryl group, and the anion of the formula (II) is a combination of any anion or anion of a cation 2+ charge in the equilibrium formula (II); wherein the concentration of the quaternary substance according to formula (II) A removal rate is exhibited for modifying at least one of the cerium oxide and Si ₃ N ₄ by the chemical mechanical polishing slurry composition. The method of claim 7, wherein the chemical mechanical polishing slurry composition comprises the following initial components: water; 0.1 to 10% by weight of the abrasive, wherein the abrasive has an average particle size of 20 to 50 nm. a colloidal ceria abrasive; 0.01 to 0.2 wt% of the halogenated quaternary ammonium compound according to formula (I), wherein R ⁸ is selected from the group consisting of -(CH ₂ ) ₂ -, -CH ₂ CHOH a group, a -(CH ₂ ) ₃ - group, X ¹ is selected from the group consisting of chlorides and bromide halides, and R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from the group consisting of -CH ₃ and -CH ₂ CH ₃ a group, wherein the anion in the formula (I) is selected from the group consisting of a chloride anion and a bromide anion; and 0.01 to 0.05% by weight of the double quaternary substance according to formula (II); wherein each A is N and R ¹ is a -(CH ₂ ) ₄ - group; and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} each a -(CH ₂ ) ₃ CH ₃ group; and the chemical mechanical polishing provided therein The slurry composition has a pH of 2 to 4. The method of claim 8, wherein the substrate comprises cerium oxide and the chemical mechanical polishing slurry composition thereof is tailored to exhibit a cerium oxide removal rate of from 200 to 3,000 Å/min. The method of claim 8, wherein the substrate comprises Si ₃ N ₄ and the chemical mechanical polishing slurry composition is trimmed to exhibit a Si ₃ N ₄ removal rate of 300 to 2,000 Å/min. The method of claim 8, wherein the substrate comprises cerium oxide and Si ₃ N ₄ and the chemical mechanical polishing slurry composition is trimmed to exhibit a 1:2 to 10:1 cerium oxide to Si ₃ N ₄ Removal rate selectivity.