Chemical mechanical polishing slurry composition for polishing metal films and polishing method using the same

Abstract

One embodiment of the present invention provides a metal film polishing slurry composition comprising an abrasive; a solvent; a pH adjuster; an oxidizing agent; a corrosion inhibitor; and a nitride film polishing promoter; wherein the polishing rate of the oxide film is maintained at a high level by the corrosion inhibitor, while the polishing rate and etching speed of the metal film are maintained at a low level and the polishing of the nitride film can be stopped.

Description

Technology Field

[0001] The present invention relates to a chemical mechanical polishing slurry composition for polishing a metal film, a method for polishing a metal film using the same, and a method for manufacturing a semiconductor device including the polishing method. Background Technology

[0003] With the increasing performance and high integration of semiconductor devices, multilayer wiring structures are becoming essential. These structures are formed by performing multiple deposition and etching processes for conductive or insulating films. After forming a specific pattern required in each layer, a surface planarization process must be performed to facilitate subsequent lithography processes. Forms of such planarization include local planarization and global planarization. Molybdenum metal, which is one of the workpieces in the above process, is used in numerous industrial applications, including microelectronic devices (e.g., interconnects, photomasks, and other uses). There is a need for novel compositions and methods for polishing molybdenum surfaces using slurries, which are consumables used as polishing materials for processing this material.

[0004] Molybdenum metal is used in numerous industrial applications, including microelectronic devices (e.g., interconnects, photomasks, and other uses). In these applications, molybdenum is initially used in excess, and subsequently, at least some of the molybdenum must be removed by polishing or lapping in a controlled manner to achieve surface properties suitable for, for example, semiconductor device manufacturing.

[0005] Buffing slurries are often used for surface finishing of materials such as metals, ceramics, glass, and semiconductors. These slurries help remove surface irregularities and make the surface of the material smooth and uniform. Related technologies for buffing slurries are diverse and can include various factors ranging from the selection of abrasives and the composition of the slurry to the buffing process itself. The aforementioned characteristics may vary depending on the applied process and can be optimized according to the properties of the specific material, the efficiency of the buffing process, and the quality of the desired surface finish.

[0006] The present invention aims to provide a composition that satisfies these commercial demands and the planarization requirements for novel materials for making more advanced devices. Specifically, the present invention was derived by the inventors due to the need to develop a slurry composition that maintains a high polishing rate for oxide and nitride films while keeping the polishing and etching rates of the metal film, specifically the molybdenum film, low.

[0007] In addition, the Chemical Mechanical Polishing (CMP) process may require a buffing CMP process performed under relatively low speed conditions for fine planarization in the later stages, in addition to the initial process of removing the target film at a high polishing speed using a bulk slurry. In particular, during this buffing process, it is necessary to polish the silicon oxide film, nitride film, or both at a high polishing speed relative to the metal film to the required level, while keeping the polishing speed of the metal film low. As the buffing process requires delicate process conditions, there is a need to develop a slurry composition equipped with a composition and conditions capable of responding to these conditions. The problem to be solved

[0009] The present invention has been devised to solve the aforementioned problems, and one embodiment of the present invention provides a slurry composition for polishing metal films.

[0010] Another embodiment of the present invention provides a method for polishing a metal film.

[0011] In addition, another embodiment of the present invention provides a method for manufacturing a semiconductor device.

[0012] The technical problems that the present invention aims to solve are not limited to those mentioned above, and other unmentioned technical problems will be clearly understood by those skilled in the art to which the present invention belongs from the description below. means of solving the problem

[0014] As a technical means to achieve the aforementioned technical problem, one aspect of the present invention provides a slurry composition for polishing a metal film comprising: an abrasive; a solvent; a pH adjuster; an oxidizing agent; a corrosion inhibitor; and a nitride film polishing promoter.

[0015] The above slurry composition can satisfy the following condition formulas 1 and 2.

[0016] [Condition 1]

[0017] B / A ≤ 1

[0018] [Condition 2]

[0019] 0.1 ≤ C / A ≤ 1.5

[0020] The above A may be the polishing speed of a silicon oxide film, the above B may be the polishing speed of a metal film, and the above C may be the polishing speed of a silicon nitride film.

[0021] The above abrasive may be a metal oxide, a metal oxide with a metal-doped or metal-coated surface, a metal oxide whose surface has been modified by a surface treatment agent, or a combination thereof.

[0022] The above metal oxide may include at least one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titania, germania, mangania, and magnesia.

[0023] The particle size of the abrasive may be a particle with a size of 5 nm or more and 130 nm or less as measured by a dynamic light scattering particle size analyzer (DLS), or a mixture of at least two types of particles including a first particle with a size of 5 to 100 nm and a second particle with a size of 20 to 130 nm.

[0024] The content of the abrasive may be 0.01 to 10 wt% with respect to the total weight of the slurry composition.

[0025] The above corrosion inhibitor may include an aromatic ring containing two or more amino groups.

[0026] The above corrosion inhibitor may be at least one selected from the following chemical formulas 1 to 3.

[0027] [Chemical Formula 1]

[0028]

[0029] [Chemical Formula 2]

[0030]

[0031] [Chemical Formula 3]

[0032]

[0033] In the above Chemical Formulas 1 to 3, R1 to R4 are each independently hydrogen, halogen, hydroxyl group, thiol group, -NO2, -NHCOR 31 (R 31 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 32 (R 32 -OCOR is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), 33 (R 33It may be any one selected from the group consisting of -SO3H, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.

[0034] The above R1 to R4 may each be independently selected from the group consisting of hydrogen, halogen, -NO2, -SO3H, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 1 to 6 carbon atoms.

[0035] The above corrosion inhibitors are 2-methyl-m-phenylenediamine, 4-chloro-m-phenylenediamine, 4-nitro-m-phenylenediamine, metaphenylene diamine-4-sulfonic acid, 4,5-dichloro-o-phenylenediamine, 3,4-dimethyl-o-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, and 2,4,6-trimethyl-1,3-phenylenediamine. It may be 2,6-Dibromo-1,4-phenylenediamine, or a combination thereof.

[0036] The above corrosion inhibitor may be in an amount of 0.0001% to 3% by weight of the molybdenum polishing slurry composition.

[0037] The above oxidizing agent may be at least one selected from the group consisting of hydrogen peroxide, hydrogen peroxide, urea, percarbonate, periodic acid, periodate, perchloric acid, perchlorate, perbromic acid, perbromate, perboric acid, perborate, permanganic acid, permanganate, persulfate, bromate, chlorate, hypochlorite, chromate, iodate, iodic acid, ammonium persulfate, benzoyl peroxide, calcium peroxide, barium peroxide, sodium peroxide, and urea peroxide.

[0038] The above oxidizing agent content may be less than 1 wt%.

[0039] The above solvent may be deionized water.

[0040] The above polishing slurry composition may have a pH range of 2 to 5.

[0041] The above pH adjuster may be sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, potassium nitrate, potassium hydroxide, imidazole, alkyl amines, alcohol amines, quaternary amine hydroxide, ammonia, or a combination thereof.

[0042] The above slurry composition may have a static etching rate (SER) of 25 Å / min or less on a molybdenum surface.

[0043] The above nitride film polishing accelerator may be at least one selected from the group consisting of phosphonic acid-based, phosphoric acid-based, and combinations thereof.

[0044] The above nitride film polishing accelerator may be nitrilotris(methylene)triphosphonic acid (NTPA), (4-aminobenzyl)phosphonic acid, (4-hydroxybenzyl)phosphonic acid, (1-aminoethyl)phosphonic acid, (2-aminoethyl)phosphonic acid, 3-phosphonopropionic acid, O-Phosphorylethanolamine, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), undecylphosphonic acid, phosphoric acid, phenylphosphate, sodium monododecylphosphate, didecylphosphate, diphenylphosphate, or a combination thereof.

[0045] The above nitride film polishing accelerator may be in an amount of 0.0005% to 4% by weight of the metal film polishing slurry composition.

[0046] The above slurry composition may be used in a buffing chemical mechanical polishing process after a metal film polishing process.

[0047] The above slurry composition may further include a second corrosion inhibitor, and the second corrosion inhibitor may include an aromatic ring comprising two or more amino groups.

[0048] The above second corrosion inhibitor may have at least one structure selected from the following chemical formulas 4 to 6.

[0049] [Chemical Formula 4]

[0050]

[0051] [Chemical Formula 5]

[0052]

[0053] [Chemical Formula 6]

[0054]

[0055] The above X1 to X5, Y1 to Y7, and Z1 to Z3 are each independently carbon, nitrogen, or sulfur, and L1 is a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, -NH-, or -NR 30 (R 30 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), and R1 to R5 and R21 to R24 are each independently hydrogen, halogen, amino group, hydroxyl group, thiol group (-SH or =S), -NO2, -NHCOR 31 (R 31 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 32 (R 32 -OCOR is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms),33 (R 33 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms, and R6 to R9, R11 to R17, and R25 to R27 are each independently hydrogen, a lone pair of electrons, a halogen, an amino group, a hydroxyl group, a thiol group (-SH or =S), -NO2, or -NHCOR. 10 (R 10 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 11 (R 11 -OCOR is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), 12 (R 12 It may be any one selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms.

[0056] At least two of the above X1 to X5 are nitrogen or sulfur, and at least one of the above R1 to R9 is a hydroxyl group, a thiol group (-SH or =S), -NO2, or -NHCOR 10 (R 10 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 11 (R 11 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), or -OCOR 12 (R 12 (It may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.)

[0057] At least one of Y1 to Y4 is nitrogen or sulfur, at least one of Y5 to Y7 is nitrogen or sulfur, and at least one of R11 to R14 is a hydroxyl group, a thiol group (-SH or =S), -NO2, or -NHCOR 10 (R 10 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 11 (R 11 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), or -OCOR 12 (R 12 (It may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.)

[0058] At least one of the above Z1 to Z3 is nitrogen or sulfur, and at least one of the above R21 to R27 is a hydroxyl group, a thiol group (-SH or =S), -NO2, -NHCOR 10 (R 10 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 11 (R 11 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), or -OCOR 12 (R 12 (It may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.)

[0059] Another aspect of the present invention provides a method for polishing a metal film, characterized by polishing the metal film using the metal film polishing slurry composition.

[0060] Another aspect of the present invention provides a method for manufacturing a semiconductor device comprising the step of polishing a metal film according to the method. Effects of the invention

[0062] According to one embodiment of the present invention, a metal film polishing slurry can be provided that achieves low corrosion of molybdenum by chemical etching, while maintaining a high polishing rate of oxide films and nitride films at a certain level, and simultaneously reducing the polishing rate and etching rate of molybdenum.

[0063] In addition, according to one embodiment of the present invention, a slurry composition applicable to improving the topography of molybdenum and polishing molybdenum barrier films can reduce surface defects such as dishing and erosion, thereby providing a metal film such as an excellent molybdenum film with finely adjusted reliability and flatness.

[0064] In addition, according to one embodiment of the present invention, the polishing speed of the metal film can be kept low, while the silicon oxide film and silver nitride film can be polished at a high polishing speed relative to the metal film to the required level, so it can be utilized as a slurry composition suitable for sensitive buffing process conditions.

[0065] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the composition of the invention described in the description or claims of the present invention. Specific details for implementing the invention

[0067] The present invention will be described in more detail below. However, the present invention may be implemented in various different forms and is not limited by the embodiments described herein, and is defined only by the claims set forth below.

[0068] Additionally, the terms used in this invention are used merely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. Throughout the specification of this invention, the term 'comprising' any component means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0069] Throughout the specification, when it is stated that a part is "connected (connected, in contact, combined)" with another part, this includes not only cases where they are "directly connected," but also cases where they are "indirectly connected" with other members interposed between them. Furthermore, when it is stated that a part "includes" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but rather allows for the inclusion of additional components.

[0070] The term “slurry composition” as used in this specification may refer to a slurry composition for polishing a target film, and the polishing may refer to Chemical Mechanical Polishing (CMP).

[0071] Unless otherwise noted, “%” as used in this specification may mean “weight%” or “wt%” in terms of content.

[0072] The terms used in this specification are used merely to describe specific embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise.

[0074] The first aspect of the present invention is,

[0075] A slurry composition for polishing a metal film is provided, comprising an abrasive; a solvent; a pH adjuster; an oxidizing agent; a corrosion inhibitor; and a nitride film polishing promoter.

[0077] Hereinafter, a slurry composition for polishing metal films according to the first aspect of the present invention will be described in detail.

[0079] In one embodiment of the present invention, the abrasive may comprise at least one selected from the group consisting of a metal oxide, a metal oxide coated with an organic or inorganic material, a metal oxide whose surface is metal-doped or metal-coated, a metal oxide whose surface is surface-modified by a surface treatment agent, and said metal oxide in a colloidal state, wherein the metal oxide may comprise at least one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titania, germania, mangania, and magnesia. The abrasive particles may preferably be a metal oxide in a colloidal state or a surface-modified metal oxide, more preferably colloidal silica, surface-modified colloidal silica, alpha-alumina, or zirconia particles.

[0080] In one embodiment of the present invention, the size of the abrasive (abrasive particle) may be the size measured by a particle size analyzer (DLS) (the size of the secondary particle), and may be a single-size particle of 1 nm to 250 nm or a mixture of two or more types of particles. Preferably, the abrasive particle is colloidal silica, and may have a size of 5 nm to 150 nm, and more preferably may have a size of 5 nm to 130 nm. In another embodiment, the particle size of the abrasive measured by a dynamic light scattering particle size analyzer (DLS) may be at least two types of mixed particles comprising a first particle of 5 to 100 nm and a second particle of 20 to 130 nm. If the abrasive particle size is less than the range described above, it may result in a decrease in the polishing speed, and if it exceeds the range described above, there may be a problem of over-polishing.

[0081] In one embodiment of the present invention, the abrasive may be in an amount of 0.005% to 10% by weight of the metal film polishing slurry composition. Preferably, the abrasive may be in an amount of 0.01% to 10% by weight of the metal film polishing slurry composition, and more preferably, in an amount of 0.05% to 5% by weight. If the abrasive particles are below the above-described range, a problem may arise in which the polishing speed is reduced, and if they exceed the above-described range, the polishing speed is too high, and surface defects may occur due to the adsorption of particles remaining on the surface caused by an increase in the number of abrasive particles.

[0082] In one embodiment of the present invention, the abrasive particles of the polishing slurry composition may be surface-treated. For example, the surface of the abrasive particles may be cationic silica in which the surface has been modified to be cationic. Through surface treatment, the polishing speed of the film can be improved, and additionally, the metal film etching speed can be further reduced.

[0083] In one embodiment of the present invention, the surface treatment agent may be an aminosilane-based surface treatment agent such that the cationic silica has a positive surface zeta potential. The surface treatment agent, which is an aminosilane compound, forms Si-O-Si covalent bonds on the surface of the silica polishing particles through condensation polymerization and can generate a cationic zeta potential on the surface of the silica polishing particles.

[0084] In one embodiment of the present invention, the surface treatment agent may be used without limitation as long as it is a surface modifier applied to conventional abrasive particles, but preferably vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl), ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3 The surface treatment agent may be at least one silane coupling agent selected from the group consisting of dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyl trimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-(trimethoxysilyl)propylsuccinic anhydride, and 3-mercaptopropyl trimethoxysilane, and more preferably, the surface treatment agent may be N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyl Trimethoxysilane, N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, and 3-mercaptopropyltrimethoxysilane may be used.

[0085] In one embodiment of the present invention, the slurry composition may include an oxidizing agent. The oxidizing agent plays a role in improving the polishing speed by oxidizing the surface of the metal film. Such an oxidizing agent is not particularly limited, but considering the oxidizing power and the stability of the slurry composition, it may be characterized by including at least one selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, urea, percarbonate, periodic acid, periodate, perchloric acid, perchlorate, perbromic acid, perbromate, perboric acid, perborate, permanganic acid, permanganate, persulfate, bromate, chlorate, hypochlorite, chromate, iodate, iodic acid, ammonium persulfate, benzoyl peroxide, calcium peroxide, barium peroxide, sodium peroxide, and urea peroxide, and preferably, hydrogen peroxide may be used as the oxidizing agent.

[0086] In one embodiment of the present invention, the oxidizing agent may be characterized as being 1 weight% or less of the metal film polishing slurry composition. Preferably, the oxidizing agent may be 0.001 weight% to less than 1 weight% of the metal film polishing slurry composition, and more preferably 0.01 weight% to 0.9 weight%. If the oxidizing agent is included in an amount exceeding 1 weight%, there is a problem that it is difficult to prevent corrosion of the metal film even if a corrosion inhibitor is included, and the polishing speed of the metal film may be set unnecessarily high, so it may be unsuitable for use as a buffing slurry.

[0087] In one embodiment of the present invention, the slurry composition for polishing a metal film may be characterized by having a pH range of 2 to 5. Preferably, the polishing slurry composition may have a pH range of 2 to 4, and more preferably, may be characterized by having a pH range of 2 to 3. If the pH of the slurry composition for polishing a metal film falls outside the above range, the polishing speed of the metal film may decrease, the surface roughness may not be uniform, and defects such as corrosion, etching, dishing, and surface unevenness may occur. In particular, if the pH of the slurry composition for polishing a metal film is basic, the etching speed may be very high, and a problem may arise where it is difficult to control the etching speed with a corrosion inhibitor. In addition, if the pH range is formed in the neutral range, the polishing speed of the oxide film decreases rapidly, and the selectivity ratio condition required in the present invention may not be satisfied.

[0088] In one embodiment of the present invention, the slurry composition for polishing a metal film may include one or more acid or base pH adjusters and buffers capable of adjusting the pH by considering the final pH of the composition, polishing rate, polishing selectivity, etc. As the pH adjuster for adjusting the pH, one capable of adjusting the pH without affecting the characteristics of the chemical mechanical polishing slurry composition may be used. In one embodiment of the present invention, the pH adjuster may be an acidic pH adjuster or a basic pH adjuster to achieve an appropriate pH.

[0089] In one embodiment of the present invention, examples of the pH adjuster may be one or more inorganic acids selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; one or more organic acids selected from the group consisting of acetic acid, citric acid, glutaric acid, glutolic acid, formic acid, lactic acid, malic acid, malonic acid, maleic acid, oxalic acid, phthalic acid, succinic acid, and tartaric acid; one or more amino acids selected from the group consisting of lysine, glycine, alanine, arginine, valine, leucine, isoleucine, methionine, cysteine, proline, histidine, phenylalanine, serine, tricin, tyrosine, aspartic acid, tryptophan, and aminobutyric acid; imidazole, alkyl amines, alcohol amines, quaternary amine hydroxide, ammonia, or a combination thereof. In particular, the pH adjuster may be triethanolamine, tetramethylammonium hydroxide (TMAH or TMAOH), or tetraethylammonium hydroxide (TEAH or TEA-OH). Additionally, as an example of the pH adjuster, it may be at least one selected from the group consisting of ammonium methyl propanol (AMP), potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium bicarbonate, sodium carbonate, triethanolamine, tromethamine, and niacinamide.

[0090] In one embodiment of the present invention, the solvent may be any solvent used in a chemical mechanical polishing slurry composition, and for example, deionized water may be used, but the present invention is not limited thereto. Additionally, preferably, ultrapure water may be used. The content of the solvent may be the remaining content excluding the content of the abrasive particles and other additional additives with respect to the entire chemical mechanical polishing slurry composition. In one embodiment of the present invention, the solvent may include water (e.g., deionized water) as an aqueous carrier and may include one or more water-miscible organic solvents. Examples of organic solvents that may be used include alcohols, e.g., propenyl alcohol, isopropyl alcohol, ethanol, 1-propanol, methanol, 1-hexanol, etc.; aldehydes, e.g., acetylaldehyde, etc.; ketones, e.g., acetone, diacetone alcohol, methyl ethyl ketone, etc.; Esters, e.g., ethyl formate, propyl formate, ethyl acetate, methyl acetate, methyl lactate, butyl lactate, ethyl lactate, etc.; sulfoxides, e.g., ethers including dimethyl sulfoxide (DMSO), tetrahydrofuran, dioxane, diglym, etc.; amides, e.g., N,N-dimethylformamide, dimethylimidazolidinone, N-methylpyrrolidone, etc.; polyhydric alcohols and derivatives thereof, e.g., ethylene glycol, glycerol, diethylene glycol, diethylene glycol monomethyl ether, etc.; and nitrogen-containing organic compounds, e.g., acetonitrile, amylamine, isopropylamine, dimethylamine, etc. may be included.

[0091] Meanwhile, the metal film according to one embodiment of the present invention may be a molybdenum film, and the oxide formed on the surface of the molybdenum may differ depending on the pH conditions. Under acidic conditions, MoO2, MoO3, and Mo2O5 may be formed on the molybdenum surface by an oxidizing agent as shown in Reaction Schemes 1 to 3 below. Specifically, under acidic conditions, oxides such as MoO2 and MoO3 are formed on the molybdenum surface by an oxidizing agent, and additionally, MoO3 may be transformed into Mo2O5. This acts as a passivation because the oxide film decomposes rather than dissolves and takes on the form of other oxide species; therefore, under acidic conditions, various types of oxide films may be found on the surface. On the other hand, under basic conditions, a large amount of MoO3 is formed on the surface of the molybdenum by hydrogen peroxide, and some of the MoO3 may react with water and be transformed into a small amount of MoO2. However, the main transformation reaction of MoO3 is rapid conversion to the weakly soluble H2MoO4, followed by MoO4, as shown in Reaction Schemes 4 and 5. 2- It may be dissolved. Therefore, under basic conditions, the main oxidation species on the molybdenum surface may consist only of undissolved MoO3.

[0092] Mo + H2O2 → MoO2 + H2[Reaction Equation 1]

[0093] 2 MoO2 + H2O2 → Mo2O5 + H2O [Reaction Equation 2]

[0094] Mo2O5 + H2O2 → 2MoO3 + H2O [Reaction Equation 3]

[0095] MoO3 + H2O → H2MoO4[Reaction Equation 4]

[0096] H2MoO4+ 2OH - → 2H2O + MoO4 2- [Reaction Equation 5]

[0098] In one embodiment of the present invention, the slurry composition may include a corrosion inhibitor. The corrosion inhibitor may include an aromatic ring comprising two or more amino groups, and in particular, the corrosion inhibitor may include at least one compound selected from Formulas 1 to 3.

[0099] [Chemical Formula 1]

[0100]

[0101] [Chemical Formula 2]

[0102]

[0103] [Chemical Formula 3]

[0104]

[0105] In the above Chemical Formulas 1 to 3, R1 to R4 are each independently hydrogen, halogen, hydroxyl group, thiol group, -NO2, -NHCOR 31 (R 31 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 32 (R 32 -OCOR is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), 33 (R 33 It may be any one selected from the group consisting of -SO3H, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.

[0106] In one embodiment of the present invention, R1 to R4 may each be independently selected from the group consisting of hydrogen, halogen, -NO2, -SO3H, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 1 to 6 carbon atoms. In the case of the structure described above, particularly since a benzene ring rather than a heterocyclic ring is connected, the electron transfer within the molecule is advantageous due to the conjugated electron distribution, and thus it can exhibit a more advantageous effect as a corrosion inhibitor.

[0107] In one embodiment of the present invention, preferably, the corrosion inhibitor is 2-methyl-m-phenylenediamine, 4-chloro-m-phenylenediamine, 4-nitro-m-phenylenediamine, metaphenylene diamine-4-sulfonic acid, 4,5-dichloro-o-phenylenediamine, 3,4-dimethyl-o-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, It may be 2,4,6-trimethyl-1,3-phenylenediamine, 2,6-dibromo-1,4-phenylenediamine, or a combination thereof, but this is a non-limiting example.

[0108] In one embodiment of the present invention, the corrosion inhibitor may be characterized as being in an amount of 0.0001% to 3% by weight of the metal film polishing slurry composition. Preferably, it may be in an amount of 0.0003% to 1% by weight, more preferably 0.001% to 1% by weight, and even more preferably 0.01% to 0.5% by weight. If the corrosion inhibitor is less than 0.0001% by weight of the metal film polishing slurry composition, the chemical etching rate is fast, resulting in high surface roughness, and the surface is not polished uniformly, which may cause problems such as difficulty in dishing, erosion, or planarization of the surface. If it exceeds 3% by weight, the chemical etching rate is very low, which may have the disadvantage of reducing the polishing rate.

[0109] In one embodiment of the present invention, the metal film polishing slurry composition may be characterized by having a static etching rate (SER) of 200 Å / min or less, preferably 100 Å / min or less, more preferably 70 Å / min or less, and in an optimally preferred embodiment 25 Å / min or less. The SER value is calculated, for example, by immersing a metal thin film wafer in a metal film polishing slurry composition at room temperature (25°C) for 10 minutes and cleaning it, then measuring the thickness of the metal wafer before and after immersion using a 4-point probe at intervals of 5 mm in all directions from the center of the wafer, and then calculating the SER value per minute. The SER value can be calculated by the following Equation 1, and the unit is Å.

[0110] [Mathematical Formula 1]

[0111]

[0113] In another embodiment of the present invention, when a surface treatment agent is further added, the static etching rate (SER) for the metal film surface can exhibit a very low value of 25 Å or less.

[0114] In one embodiment of the present invention, the metal film polishing slurry composition may be characterized by having a metal film polishing rate (polishing speed) of 10 to 550 Å / min. The metal film polishing rate using the metal film polishing slurry composition may preferably be 15 to 500 Å / min. However, this value varies depending on the composition of the slurry composition and is not limited thereto; it may simply mean the polishing rate at the optimal composition as one embodiment, and above all, it may be set to obtain an optimal value by considering the relationship with the static etching rate described above.

[0115] In one embodiment of the present invention, the slurry composition may satisfy the following condition formulas 1 and 2.

[0116] [Condition 1]

[0117] B / A ≤ 1

[0118] [Condition 2]

[0119] 0.1 ≤ C / A ≤ 1.5

[0120] The above A may be the polishing rate of a silicon oxide film, the above B may be the polishing rate of a metal film, and the above C may be the polishing rate of a silicon nitride film. Here, the polishing rates may each be expressed in units of Å / min.

[0121] In one embodiment of the present invention, satisfying B / A of 1 or less means that the polishing speed of the metal film is less than or equal to the polishing speed of the silicon oxide film. In a typical bulk metal film slurry composition, the composition is prepared so that the polishing speed of the metal film is greater than that of the oxide film. Therefore, if this is utilized in a buffing process, the metal film may be polished more unnecessarily, and problems such as dishing may occur.

[0122] In one embodiment of the present invention, C / A ≤ 1.5, preferably C / A ≤ 1.25, more preferably C / A ≤ 1.1, even more preferably C / A ≤ 1.0, and 0.01 ≤ C / A, preferably 0.05 ≤ C / A, more preferably 0.1 ≤ C / A, which means that the composition has a selectivity ratio that allows for polishing a certain level of metal film during a buffing process, while particularly polishing oxide films and nitride films relatively more.

[0123] In one embodiment of the present invention, a nitride film polishing accelerator may be included in order to maintain a high polishing speed of the nitride film along with the oxide film.

[0124] In one embodiment of the present invention, the nitride film polishing accelerator may be at least one selected from the group consisting of phosphonic acid-based, phosphoric acid-based, and combinations thereof. For example, the nitride film polishing accelerator may be nitrilotris(methylene)triphosphonic acid (NTPA), (4-aminobenzyl)phosphonic acid, (4-hydroxybenzyl)phosphonic acid, (1-aminoethyl)phosphonic acid, (2-aminoethyl)phosphonic acid, 3-phosphonopropionic acid, O-Phosphorylethanolamine, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), undecylphosphonic acid, phosphoric acid, phenylphosphate, sodium monododecyl phosphate, didecyl phosphate, diphenyl phosphate, or a combination thereof.

[0125] In one embodiment of the present invention, the nitride film polishing accelerator may be in an amount of 0.0001% to 10% by weight of the metal film polishing slurry composition. Preferably, the nitride film polishing accelerator may be in an amount of 0.0005% to 4% by weight of the metal film polishing slurry composition, and more preferably, in an amount of 0.005% to 2% by weight. If the amount is less than the above-described range, there is a problem that the nitride film polishing speed does not increase as much as required, and if the amount exceeds the above-described range, there may be a problem that it may act as an impurity itself, thereby causing unexpected changes in the physical properties of the slurry composition.

[0126] In one embodiment of the present invention, a second corrosion inhibitor may be further included, and the second corrosion inhibitor may have at least one structure selected from the following chemical formulas 4 to 6.

[0127] [Chemical Formula 4]

[0128]

[0129] [Chemical Formula 5]

[0130]

[0131] [Chemical Formula 6]

[0132]

[0133] The above X1 to X5, Y1 to Y7, and Z1 to Z3 are each independently carbon, nitrogen, or sulfur, and L1 is a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, -NH-, or -NR 30 (R 30 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), and R1 to R5 and R21 to R24 are each independently hydrogen, halogen, amino group, hydroxyl group, thiol group (-SH or =S), -NO2, -NHCOR 31 (R 31(is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 32 (R 32 -OCOR is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), 33 (R 33 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms, and R6 to R9, R11 to R17, and R25 to R27 are each independently hydrogen, a lone pair of electrons, a halogen, an amino group, a hydroxyl group, a thiol group (-SH or =S), -NO2, or -NHCOR. 10 (R 10 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 11 (R 11 -OCOR is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), 12 (R 12It may be any one selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms.

[0134] In one embodiment of the present invention, in Formula 4, at least two of X1 to X5 are nitrogen or sulfur, and at least one of R1 to R9 is a hydroxyl group, a thiol group (-SH or =S), -NO2, or -NHCOR 10 (R 10 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 11 (R 11 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), or -OCOR 12 (R 12 (It may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.) That is, in the case of the pentagonal heteroring in the structure of Chemical Formula 1, it is a ring structure containing two or more heteroatoms, and can be viewed as a structure in which one specific substituent is substituted on a benzene ring or a heteroring. In the case of such a structure, particularly because a benzene ring rather than a heteroring is connected, the electron transfer within the molecule is advantageous due to the conjugated electron distribution, so it can exhibit a more advantageous effect as a corrosion inhibitor.

[0135] In one embodiment of the present invention, in Formula 5, at least one of Y1 to Y4 is nitrogen or sulfur, at least one of Y5 to Y7 is nitrogen or sulfur, and at least one of R11 to R14 is a hydroxyl group, a thiol group (-SH or =S), -NO2, or -NHCOR 10 (R 10 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 11 (R 11 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), or -OCOR 12 (R 12 (It may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.) That is, in the structure of Chemical Formula 2, both fused ring structures may be heterocyclic structures containing heteroatoms, and the hexagonal aromatic heterocyclic structure can be viewed as a structure in which one specific substituent is substituted. In the case of such a structure, if it contains an electron-attracting substituent (e.g., =O), it has the characteristic of reduced electron distribution within the molecule, so its performance as a corrosion inhibitor may be reduced; therefore, the corrosion inhibitory effect can be optimized only if the structural characteristics described above are satisfied.

[0136] In one embodiment of the present invention, in Formula 6, at least one of Z1 to Z3 is nitrogen or sulfur, and at least one of R21 to R27 is a hydroxyl group, a thiol group (-SH or =S), -NO2, or -NHCOR 10 (R 10 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 11 (R 11 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), or -OCOR 12 (R 12(It may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.) That is, in the structure of Chemical Formula 3, the fused pentagonal aromatic ring may be a heterocyclic structure containing heteroatoms, and the hexagonal or pentagonal aromatic heterocyclic ring may be viewed as a structure in which at least one specific substituent is substituted. In the case of such a structure, particularly since a benzene ring rather than a heterocyclic ring is connected, the electron transfer within the molecule is advantageous due to the conjugated electron distribution, so it can exhibit a more advantageous effect as a corrosion inhibitor.

[0137] In one embodiment of the present invention, preferably, the second corrosion inhibitor may be 6-aminobenzothiazole, adenine, 1-phenyl-1H-tetrazole-5-thiol, or a combination thereof.

[0138] In one embodiment of the present invention, the second corrosion inhibitor may be characterized as being in an amount of 0.0001% to 3% by weight of the metal film polishing slurry composition. Preferably, it may be in an amount of 0.001% to 2% by weight.

[0139] In one embodiment of the present invention, when a second corrosion inhibitor is included, the content of the second corrosion inhibitor per 100 parts by weight of the corrosion inhibitor may be additionally included in an amount of 5 to 40 parts by weight, preferably 10 to 30 parts by weight. If the above-described range is exceeded, it acts as an impurity and may have an adverse effect in terms of polishing speed or static etching speed of the metal film.

[0140] According to one embodiment of the present invention, when a second corrosion inhibitor is additionally added, a further suppressed static etching rate of less than 10 Å / min, i.e., a corrosion prevention effect, can be confirmed.

[0141] In addition, in one embodiment of the present invention, the slurry composition may further include, if necessary, additives such as polymer compounds and dispersants commonly used in the industry in addition to the components described above.

[0143] The second aspect of the present invention is,

[0144] A method for polishing a metal film is provided, characterized by polishing the metal film using the above-described metal film polishing slurry composition.

[0146] Detailed explanations have been omitted for parts that overlap with the first aspect of the present invention; however, the content described in the first aspect of the present invention may be applied equally even if such explanations are omitted in the second aspect.

[0148] Hereinafter, according to the second aspect of the present invention

[0149] The method for polishing metal films is explained in detail.

[0151] In one embodiment of the present invention, the method for polishing the metal film may be characterized by polishing the metal film using the polishing slurry composition. Specifically, the method for polishing the metal film may include the step of contacting the surface of a metal-containing substrate with a chemical mechanical polishing composition, which is the metal film polishing slurry composition; and the step of inducing relative motion between the polishing pad and the substrate while maintaining a portion of the polishing slurry composition in contact with the surface between the polishing pad and the substrate for a time sufficient to abrade at least a portion of the metal from the substrate.

[0152] Since the above polishing method utilizes the above polishing slurry composition, the etching rate can be controlled under high-concentration oxidizing agent conditions, thereby lowering metal corrosion while improving the metal polishing rate, and it can be confirmed that the metal topography is improved.

[0153] In one embodiment of the present invention, the polishing method is particularly suitable for use with a chemical-mechanical polishing apparatus. Typically, the CMP apparatus comprises a platen (which moves during use and has a velocity induced by orbital, linear, and / or annular motion), a polishing pad (which contacts the platen and moves together with the platen during movement), and a carrier (which holds a substrate to be polished in contact with the pad and moves relative to the surface of the polishing pad). A CMP composition is typically pumped onto the polishing pad to assist in the polishing process. Polishing of the substrate is achieved by the combined abrasive action of the moving polishing pad and the CMP composition of the present invention present on the polishing pad, which abrades at least a portion of the surface of the substrate and thereby polishes the surface. The substrate may be flattened or polished by the CMP composition of the present invention using any suitable polishing pad (e.g., polishing surface). Suitable polishing pads include, for example, woven and nonwoven polishing pads. Additionally, suitable polishing pads may comprise any suitable polymer having various densities, hardness, thickness, compressibility, ability to rebound upon compression, and compression modulus. Suitable polymers may include, for example, polyvinyl chloride, polyvinyl fluoride, nylon, fluorocarbon, polycarbonate, polyester, polyacrylate, polyether, polyethylene, polyamide, polyurethane, polystyrene, polypropylene, copolymerized products thereof, and mixtures thereof.

[0154] The third aspect of this invention is,

[0155] A method for manufacturing a semiconductor device is provided, comprising the step of polishing a metal film according to the above method.

[0157] Detailed explanations have been omitted for parts that overlap with the first and second aspects of the present invention, but the explanations for the first and second aspects of the present invention may be applied in the same way even if such explanations are omitted in the third aspect.

[0159] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0161] Performance evaluation method

[0162] The performance of the slurry composition was evaluated as follows.

[0163] - Evaluation Method: CMP polishing rate evaluation, static etching rate (SER) evaluation,

[0164] - Wafer: Molybdenum wafer 4 x 4 (cm)

[0165] - Sintering conditions

[0166] - Pad: IC1010

[0167] - Polishing conditions

[0168]

[0169] - E / R temperature condition: 45℃

[0170] - Evaluation equipment, thin film measurement equipment: Poly-400, 4-point probe

[0171] The results of each evaluation are as follows.

[0173] Example 1: Analysis of Corrosion Inhibition Effect by Corrosion Inhibitor

[0174] A slurry composition was prepared by adding hydrogen peroxide as an oxidizing agent and each corrosion inhibitor to deionized water as a solvent according to the amounts listed in Table 1 below, adding colloidal silica with a particle size of 70 nm as an abrasive, stirring, and adjusting the pH to 2. The polishing rate of the silicon oxide film, silicon nitride film, and molybdenum film, and the etching rate of the molybdenum film were measured and are shown in Table 1 below.

[0175] division Abrasive particle size (nm) Particle concentration (wt%) pH H2O2 concentration (wt%) Types of corrosion inhibitors Corrosion inhibitor concentration (wt%) Types of SiN polishing accelerators SiN polishing accelerator concentration (wt%) Oxide RR (Å / min) SiN RR (Å / min) Mo RR (Å / min) Mo ER (Å / min) Mo / Oxide SiN / Oxide Comparative Example 1 70 1 2 0.3 - - - - 541 45 489 194 0.904 0.083 Comparative Example 2 70 1 2 0.3 Tetrazole 0.05 - - 557 44 361 63 0.648 0.079 Comparative Example 3 70 1 2 0.3 2-Mercaptothiazoline 0.05 - - 529 42 377 104 0.713 0.079 Comparative Example 4 70 1 2 0.3 Pyrrole 0.05 - - 533 44 460 178 0.863 0.083 Comparative Example 5 70 1 2 0.3 Glycine 0.05 - - 548 40 404 125 0.737 0.073 Comparative Example 6 70 1 2 0.3 o-Phenylenediamine 0.05 - - 544 45 91 4 0.167 0.083 Comparative Example 7 70 1 2 0.3 2-Methyl-m-phenylenediamine 0.05 - - 553 48 107 8 0.193 0.087 Example 1 70 1 2 0.3 o-Phenylenediamine 0.05 3-Phosphonopropionic acid 0.05 598 214 107 4 0.179 0.358 Example 2 70 1 2 0.3 o-Phenylenediamine 0.05 1-Aminoethylphosphonic acid 0.05 601 234 112 5 0.186 0.389 Example 3 70 1 2 0.3 o-Phenylenediamine 0.05 NTPA 0.05 557 258 88 5 0.158 0.463 Example 4 70 1 2 0.3 2-Methyl-m-phenylenediamine 0.05 NTPA 0.05 571 251 99 6 0.173 0.440 Example 5 70 1 2 0.3 o-Phenylenediamine 0.05 NTPA 0.12 557 537 110 5 0.197 0.964 Example 6 70 1 2 0.3 o-Phenylenediamine 0.05 3-Phosphonopropionic acid 0.12 605 522 109 5 0.180 0.863

[0176] Referring to Table 1 above, it was confirmed that the overall molybdenum etching rate decreased, even by a small amount, when the corrosion inhibitor was included compared to when no corrosion inhibitor was added, as in Comparative Example 1. However, the slurry compositions of Comparative Examples 2 to 5 showed an etching rate exceeding 60 Å / min, so no significant corrosion prevention effect could be confirmed. As in Comparative Examples 6 and 7, even when satisfying the corrosion inhibitor structure of the present invention, if the nitride film polishing accelerator was not included, the nitride film polishing rate was low at less than 50 Å / min, so the expected effect of the present invention could not be satisfied. On the other hand, in the case of Examples 1 to 6, which satisfy the corrosion inhibitor structure of the present invention and include a nitride film polishing accelerator, it was confirmed that the overall static etching rate (SER) was 10 Å / min or less, and the polishing rates of the oxide film and nitride film were relatively high. In particular, through Examples 5 and 6, it was confirmed that when the content of the nitride film polishing accelerator is increased, the polishing speed of the nitride film can be increased to a level similar to that of the oxide film, or in some cases, even to a higher level.

[0178] Example 2: Analysis of polishing speed of composition according to abrasive size

[0179] In order to determine the most appropriate particle size range for the abrasive (abrasive particles) of the slurry composition, the etching rate and polishing rate of the molybdenum film, and the polishing rate performance of the silicon oxide film and nitride film were verified by increasing the particle size as shown in Table 2 below.

[0180] division Abrasive particle size (nm) Particle concentration (wt%) pH H2O2 concentration (wt%) Corrosion inhibitor Corrosion inhibitor concentration (wt%) SiN polishing accelerator SiN polishing accelerator concentration (wt%) Oxide RR (Å / min) SiN RR (Å / min) Mo RR (Å / min) Mo ER (Å / min) Mo / Oxide SiN / Oxide Example 7 20 1 2 0.3 o-Phenylenediamine 0.05 NTPA 0.05 121 41 24 4 0.198 0.339 Example 8 50 1 2 0.3 o-Phenylenediamine 0.05 NTPA 0.05 371 158 70 5 0.189 0.426 Example 9 70 1 2 0.3 o-Phenylenediamine 0.05 NTPA 0.05 557 258 88 5 0.158 0.463 Example 10 100 1 2 0.3 o-Phenylenediamine 0.05 NTPA 0.05 404 171 70 5 0.173 0.423

[0181] Referring to Table 2, it was generally predicted that increasing the size of the polishing particles would increase the polishing speed regardless of the film type; however, in the case of Example 10, it was confirmed that the overall polishing speed actually decreased compared to Example 9, so it was confirmed that the optimal effect was observed in the particle size range of 10 to 100 nm, particularly in the particle size range of 45 to 75 nm.

[0183] Example 3: Performance evaluation of slurry composition according to pH and hydrogen peroxide concentration

[0184] In order to determine the most appropriate ranges for each according to the pH range and oxidant content range of the slurry composition, the etching rate and polishing rate of the molybdenum film, and the polishing rate performance of the silicon oxide film and nitride film were verified as shown in Table 3 below.

[0185]

[0187] Referring to Table 3, it was confirmed that the selectivity required by the present invention is satisfied only in the pH range of 4.5 or lower, particularly in the range of 2 to 4, according to Examples 11 and 12. By examining Examples 13 and 14 and confirming the trend of selectivity characteristics according to the oxidant concentration, it was seen that the selectivity condition of the present invention can be satisfied only when the condition of the oxidant concentration being less than 1% is met.

[0189] Example 4: Performance evaluation of slurry composition according to abrasive particle concentration

[0190] To determine the most appropriate abrasive particle concentration range of the slurry composition, the etching rate and polishing rate of the molybdenum film, and the polishing rate performance of the silicon oxide film and nitride film were verified as shown in Table 4 below.

[0191] division Abrasive particle size (nm) Particle concentration (wt%) pH H2O2 concentration (wt%) Corrosion inhibitor Corrosion inhibitor concentration (wt%) SiN polishing accelerator SiN polishing accelerator concentration (wt%) Oxide RR (Å / min) SiN RR (Å / min) Mo RR (Å / min) Mo ER (Å / min) Mo / Oxide SiN / Oxide Example 15 70 0.1 2 0.3 o-Phenylenediamine 0.05 NTPA 0.05 99 41 18 7 0.182 0.414 Example 16 70 3 2 0.3 o-Phenylenediamine 0.05 NTPA 0.05 887 370 155 5 0.175 0.417 Example 17 70 5 2 0.3 o-Phenylenediamine 0.05 NTPA 0.05 1322 600 231 5 0.175 0.454

[0193] Referring to Table 4, at a polishing particle concentration of 0.1 to 5 weight%, both the selectivity and corrosion prevention effects of the present invention could be confirmed.

[0195] Example 5: Performance evaluation of slurry composition according to surface treatment of abrasive particles

[0196] Hydrogen peroxide as an oxidizing agent and 6-Aminobenzothiazole as a corrosion inhibitor were added to deionized water as a solvent according to the amounts listed in Table 5 below, NTPA as a polishing accelerator for the nitride film, and surface-modified colloidal silica of the particle size listed therein (the surface of the abrasive is modified by including an aminosilane-based surface treatment agent disclosed in the detailed description of the present invention as a surface treatment agent) as an abrasive, stirred, and the pH was adjusted to prepare a slurry composition. The polishing rate of the molybdenum film, the static etching rate, the polishing rate of the silicon oxide film, and the polishing rate of the silicon nitride film were measured and shown in Table 5 below.

[0198] division Abrasive particle size (nm) Particle concentration (wt%) pH H2O2 concentration (wt%) Corrosion inhibitor Corrosion inhibitor concentration (wt%) SiN polishing accelerator SiN polishing accelerator concentration (wt%) Oxide RR (Å / min) SiN RR (Å / min) Mo RR (Å / min) Mo ER (Å / min) Mo / Oxide SiN / Oxide Example 18 50nm amino silane surface-treated 1 2 0.3 o-Phenylenediamine 0.05 NTPA 0.05 409 188 72 5 0.176 0.460 Example 19 70nm amino silane surface-treated 1 2 0.3 o-Phenylenediamine 0.05 NTPA 0.05 656 283 125 4 0.191 0.431

[0200] Referring to Table 5, as can be seen in Examples 18 and 19, it was confirmed that when the abrasive material is surface modified, the corrosion prevention effect on the molybdenum film is maximized.

[0202] Example 6: Performance evaluation of slurry composition with addition of additional corrosion inhibitor

[0203] To observe the effect of adding a second corrosion inhibitor, a slurry composition was prepared as shown in Table 6 below, and the polishing speed of the molybdenum film, static etching speed, and polishing speed performance of the silicon oxide film and nitride film were verified.

[0204]

[0205] Referring to Table 6, it was confirmed that when the content of the second corrosion inhibitor is additionally included in the corrosion inhibitor at a ratio of 10 to 30 parts by weight per 100 parts by weight, the static etching rate is 10 Å / min or less, more specifically 5 Å / min or less, thereby maximizing the corrosion prevention effect.

[0207] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will understand that other specific forms can be easily modified without altering the technical spirit or essential features of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single unit may be implemented in a distributed manner, and components described as distributed may likewise be implemented in a combined form.

[0208] The scope of the present invention is defined by the claims set forth below, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of the present invention.

Claims

Claim 1 Abrasive; Solvent; pH Adjuster; Oxidizer; 2-Methyl-m-phenylenediamine, 4-Chloro-m-phenylenediamine, 4-Nitro-m-phenylenediamine, Metaphenylene Diamine-4-Sulfonic Acid, 4,5-Dichloro-o-phenylenediamine, 3,4-Dimethyl-o-phenylenediamine, 2,5-Dimethyl-1,4-phenylenediamine, 2,4,6-Trimethyl-1,3-phenylenediamine, A slurry composition for polishing a metal film, comprising: a corrosion inhibitor which is 2,6-Dibromo-1,4-phenylenediamine or a combination thereof; and at least one nitride film polishing accelerator selected from the group consisting of phosphonic acid-based, phosphoric acid-based, and combinations thereof; Claim 2 A slurry composition for polishing a metal film according to claim 1, characterized in that the slurry composition satisfies the following condition formulas 1 and 2. [Condition Formula 1] B / A ≤ 1 [Condition Formula 2] 0.1 ≤ C / A ≤ 1.5 (wherein A is the polishing speed of a silicon oxide film, B is the polishing speed of a metal film, and C is the polishing speed of a silicon nitride film) Claim 3 A slurry composition for polishing a metal film according to claim 1, characterized in that the abrasive is a metal oxide, a metal oxide with a surface that is metal-doped or metal-coated, a metal oxide whose surface has been modified by a surface treatment agent, or a combination thereof. Claim 4 A slurry composition for polishing a metal film according to claim 3, characterized in that the metal oxide comprises at least one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titania, germania, mangania, and magnesia. Claim 5 A slurry composition for polishing a metal film according to claim 1, characterized in that the particle size of the abrasive material measured by a dynamic light scattering particle size analyzer (DLS) is 5 nm or more and 130 nm or less, or comprises at least two types of mixed particles including a first particle with a size of 5 to 100 nm and a second particle with a size of 20 to 130 nm. Claim 6 A slurry composition for polishing a metal film according to claim 1, characterized in that the content of the abrasive is 0.01 to 10 wt% with respect to the total weight of the slurry composition. Claim 7 delete Claim 8 delete Claim 9 delete Claim 10 delete Claim 11 A metal film polishing slurry composition according to claim 1, characterized in that the corrosion inhibitor is 0.0001% to 3% by weight of the metal film polishing slurry composition. Claim 12 A slurry composition for polishing a metal film according to claim 1, wherein the oxidizing agent is at least one selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, urea, percarbonate, periodic acid, periodate, perchloric acid, perchlorate, perbromic acid, perbromate, perboric acid, perborate, permanganic acid, permanganate, persulfate, bromate, chlorate, hypochlorite, chromate, iodate, iodic acid, ammonium persulfate, benzoyl peroxide, calcium peroxide, barium peroxide, sodium peroxide, and urea peroxide. Claim 13 A slurry composition for polishing a metal film according to claim 1, characterized in that the oxidizing agent content is less than 1 wt%. Claim 14 A slurry composition for polishing a metal film according to claim 1, wherein the solvent is deionized water. Claim 15 A metal film polishing slurry composition according to claim 1, characterized in that the polishing slurry composition has a pH range of 2 to 5. Claim 16 A slurry composition for polishing a metal film according to claim 1, characterized in that the pH adjuster is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, potassium nitrate, potassium hydroxide, imidazole, alkyl amines, alcohol amines, quaternary amine hydroxide, ammonia, or a combination thereof. Claim 17 A slurry composition for polishing a metal film according to claim 1, characterized in that the slurry composition has a static etching rate (SER) of 25 Å / min or less for a molybdenum surface. Claim 18 delete Claim 19 A slurry composition for polishing a metal film according to claim 1, wherein the nitride film polishing accelerator is nitrilotris(methylene)triphosphonic acid (NTPA), (4-aminobenzyl)phosphonic acid, (4-hydroxybenzyl)phosphonic acid, (1-aminoethyl)phosphonic acid, (2-aminoethyl)phosphonic acid, 3-phosphonopropionic acid, O-Phosphorylethanolamine, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), undecylphosphonic acid, phosphoric acid, phenylphosphate, sodium monododecyl phosphate, didecyl phosphate, diphenyl phosphate, or a combination thereof. Claim 20 A metal film polishing slurry composition according to claim 1, characterized in that the nitride film polishing accelerator is 0.0005 weight% to 4 weight% of the metal film polishing slurry composition. Claim 21 A slurry composition for polishing a metal film according to claim 1, further comprising a second corrosion inhibitor, wherein the second corrosion inhibitor comprises an aromatic ring comprising two or more amino groups. Claim 22 A slurry composition for polishing a metal film according to claim 1, further comprising a second corrosion inhibitor, wherein the second corrosion inhibitor has a structure selected from at least one of the following chemical formulas 4 to 6. [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] (The above X1 to X5, Y1 to Y7, Z1 to Z3 are each independently carbon, nitrogen, or sulfur, and L1 is a single bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, -NH-, or -NR 30 (R 30 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), and R1 to R5 and R21 to R24 are each independently hydrogen, halogen, amino group, hydroxyl group, thiol group (-SH or =S), -NO2, -NHCOR 31 (R 31 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 32 (R 32 -OCOR is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), 33 (R 33 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms, and R6 to R9, R11 to R17, R25 to R27 are each independently hydrogen, a non-covalent electron pair, a halogen, an amino group, a hydroxyl group, a thiol group (-SH or =S), -NO2, -NHCOR 10 (R 10 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 11 (R 11 -OCOR is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), 12 (R 12 (is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), any one selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms) Claim 23 A method for polishing a metal film characterized by polishing the metal film using the metal film polishing slurry composition of claim 1. Claim 24 A method for manufacturing a semiconductor device comprising the step of polishing a metal film according to the method of claim 23.

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