Composite particle for polishing metal films and polishing slurry composition comprising the same

Abstract

The present invention provides a composite particle for polishing a metal film, characterized by comprising an inorganic particle, wherein the surface of the inorganic particle is modified with one or more of a silane compound containing an alkyne group and a silane compound containing an alkyl chloride group, and a polishing slurry composition comprising the composite particle for polishing a metal film. The polishing slurry composition comprising the composite particle for polishing a metal film is used for polishing a metal film, and can exhibit an excellent polishing rate and physical properties after polishing while achieving a control effect to inhibit polishing of the metal film.

Description

Technology Field

[0001] The following examples relate to composite particles for polishing metal films and polishing slurry compositions containing the same. Background Technology

[0003] Recently, chemical mechanical polishing (CMP) processes for various thin films constituting devices have become increasingly necessary in the semiconductor and display industries.

[0004] The Chemical Mechanical Polishing (CMP) process refers to a process of flattening the surface of a semiconductor wafer by contacting it with a polishing pad and using a slurry containing abrasives and various compounds while performing rotational motion. Generally, metal polishing processes involve metal oxides (MO) by means of an oxidizing agent x It is known that the process of forming the metal oxide and the process of removing the formed metal oxide by abrasive particles occur repeatedly.

[0005] An integrated circuit consists of hundreds of active devices formed within or on a silicon support, which are short-circuited and interconnected to form a functional circuit, and each layer of the active devices is connected by a multi-level interconnection method. The interconnection layer within the integrated circuit generally has metallization levels connected to a first metal layer, an interconnection layer, a second metal layer, an interconnection layer, and a third metal layer. Dielectrics, such as doped and undoped silicon dioxide (SiO2), used as interconnection layers are used to electrically short-circuit different levels of metal layers within the silicon support.

[0006] In the fabrication of integrated circuits and other electronic devices, multilayers of conductive, semiconducting, and dielectric materials are deposited on or removed from the surface of a substrate. Thin layers of conductive, semiconducting, and dielectric materials can be deposited by numerous deposition techniques. Common deposition techniques in modern fabrication include physical vapor deposition (PVD), also known as sputtering; chemical vapor deposition (CVD); plasma-enhanced chemical vapor deposition (PECVD); and electrochemical plating (ECP).

[0007] Because layers of materials are deposited and removed continuously, the top surface of the substrate may not be flat across the entire surface and requires planarization. Surface planarization, or surface "polishing," is a process of removing material from the surface of a substrate to form a generally flat and smooth surface. Planarization is useful for removing undesirable surface features and defects, such as rough surfaces, aggregated materials, crystal lattices, damaged areas, scratches, and contaminated layers or materials. Additionally, planarization is useful for forming features on the substrate by removing excess deposited material used to fill the features and provide a flat surface for subsequent steps of metallization and processing.

[0008] The metal CMP process is known to involve a repeated process in which abrasive particles remove an oxide film formed by an oxidizing agent. Therefore, to improve the polishing rate, the slurry is designed by considering factors such as accelerating the oxidation process or efficiently removing the formed oxide film. An easy method to improve the polishing speed is to increase the concentration of the oxide that corrodes the metal; however, as the corrosion rate increases, corrosion occurs even in areas where wiring layers must be formed for the electrical characteristics of the device, such as seams or contacts, which can actually reduce the reliability and yield of the device. Consequently, metal corrosion inhibitors have been added to suppress the degree of metal corrosion, but there have been limitations in controlling the corrosion level. The problem to be solved

[0010] To solve the above-mentioned problems, the purpose is to provide a composite particle for polishing a metal film, characterized by including an inorganic particle, wherein the surface of the inorganic particle is modified by one or more of a silane compound containing an alkyne group and a silane compound containing an alkyl chloride group, and a polishing slurry composition including the composite particle for polishing a metal film.

[0012] However, the problems that the invention seeks to solve are not limited to those mentioned above, and other unmentioned problems will be clearly understood by a person skilled in the art from the description below. means of solving the problem

[0014] According to one embodiment, a composite particle for polishing a metal film is provided, comprising an inorganic particle, wherein the surface of the inorganic particle is modified with one or more of a silane compound containing an alkyne group and a silane compound containing an alkyl chloride group.

[0015] The above inorganic particles may include one or more of the metal oxide and the metal oxide in a colloidal state.

[0016] In addition, the metal oxide may include one or more of silica, ceria, zirconia, alumina, titania, barium titania, germania, mangania, and magnesia.

[0017] The average diameter of the above inorganic particles may be 5 nm to 300 nm.

[0018] The silane compounds containing the alkyne group mentioned above are 3-(trimethoxysilyl)propylalkyne, 3-(trimethoxysilyl)propyl-1-phenylalkyne, 3-(trimethoxysilyl)propyl-1-phenyl-1-hexane, 3-(trimethoxysilyl)propyl-1-phenyl-1-hexyne, 3-(trimethoxysilyl)propyl-1-cyclohexylalkyne, 3-(trimethoxysilyl)propyl-1-bromoalkyne, and 3-(trimethoxysilyl)propyl-1-pentane (3-(Trimethoxysilyl)propyl-1-pentyne), 3-(Trimethoxysilyl)propyl-1-heptyne), 3-(Trimethoxysilyl)propyl-1-octyne), 3-(Trimethoxysilyl)propyl-1-nonyne), 3-(Trimethoxysilyl)propyl-1-decyne), 3-(Trimethoxysilyl)propyl-4-octyne), 3-(Trimethoxysilyl)propyl-3-hexane It may include one or more of (3-(Trimethoxysilyl)propyl-3-heptyne), 3-(Trimethoxysilyl)propyl-3-heptyne, 3-(Trimethoxysilyl)propyl-2-octyne, and 3-(Trimethoxysilyl)propyl-2-heptyne.

[0019] The silane compounds containing the above-mentioned alkyl chloride group are trimethylchlorosilane (TMCS), triethylchlorosilane (TECS), triphenylchlorosilane (TPClS), trichloro(methyl)silane (Trichloromethylsilane, TCMS), trichlorobutylsilane (Trichlorobutylsilane), trichloroacetylsilane (TCAS), trichloropropylsilane (TCPS), trichloromethyl ether silane (TCMES), trichlorobenzylsilane (TCBS), trichloromethylamine silane (TCMA), trichlorophenylsilane (TCPSSi), and trichlorobutylmethylsilane (TCBMS). It may include one or more of trichlorohexylsilane (TCHS), trichloroisobutylsilane (TCIBs), and trichloromethylbenzylsilane (TCMBS).

[0020] The above metal film may include one or more of a metal, a metal nitride, a metal oxide, and a metal alloy.

[0021] The metal in the above metal, metal nitride, metal oxide, and metal alloy may include one or more of copper (Cu), tungsten (W), molybdenum (Mo), indium (In), tin (Sn), silicon (Si), titanium (Ti), vanadium (V), gadolium (Ga), manganese (Mn), iron (Fe), cobalt (Co), zinc (Zn), zirconium (Zr), hafnium (Hf), aluminum (Al), niobium (Nb), nickel (Ni), chromium (Cr), tantalum (Ta), and ruthenium (Ru).

[0022] Meanwhile, according to one embodiment, a polishing slurry composition comprising composite particles for polishing a metal film and a corrosion inhibitor is provided.

[0023] The above corrosion inhibitor may include one or more of a compound containing an alkyne group and a compound containing an azide group.

[0024] The above-mentioned composite particles for polishing metal films include inorganic particles, and the surface of the inorganic particles may be modified with one or more of a silane compound containing an alkyne group and a silane compound containing an alkyl chloride group.

[0025] In addition, the compound containing the alkyne group may include one or more of acetylene, phenylacetylene, trimethylsilylacetylene, 1-octadecylacetylene, 1-hexadecylacetylene, 2-acetylhexadiene, 4-octadecene, tributylacetylene, 1-butylacetylene, 1-propylacetylene, 2-methoxy-1-hex-1-phosphine, 1-methyl-1-hex-1-phosphine, 1,4-dimethoxy-2-butylacetylene, vinylacetylene, and 1,3-dipentylacetylene.

[0026] The compound containing the azide group may include one or more of benzyl azide, ethyl azide, methyl azide, 4-methoxybenzyl azide, 2-chlorobenzyl azide, 3-bromobenzyl azide, N-methyl azide, N-butyl azide, benzoyl azide, 2-hydroxybenzyl azide, 4-aminophenyl azide, 3-methoxybenzyl azide, 4-chlorobenzyl azide, 4-acetylphenyl azide, and phenylenediamine azide.

[0027] Meanwhile, the composite particles for polishing the metal film may be included in the polishing slurry composition in an amount of 0.01% to 20% by weight.

[0028] The above polishing slurry composition may further include one or more of an oxidizing agent, a chelating agent, and a pH adjuster.

[0029] The above oxidizing agent is hydrogen peroxide, urea, hydrogen peroxide, urea, percarbonate, periodic acid, periodate, perchloric acid, perchlorate, perbromic acid, perbrodate, perboric acid, perborate, potassium permanganate, sodium perborate, permanganic acid, permanganate, persulfate, bromate, chlorite, chlorate, chromate, dichromate, iodate, iodic acid, ammonium persulfate, benzoyl peroxide, calcium peroxide, barium peroxide, sodium peroxide, dioxygenyl, ozone, ozonide, nitrate, hypochlorite, It may include one or more of hypohalite, chromium trioxide, pyridinium chlorochromate, nitrous oxide, monopersulfate, dipersulfate, and sodium peroxide.

[0030] The content of the oxidizing agent may be 0.01% to 5% by weight relative to the total weight of the polishing slurry composition.

[0031] The above chelating agent may include one or more of amino acids and organic acids, wherein the amino acid includes one or more of glycine, arginine, lysine, histidine, aspartic acid, glutamic acid, asparagine, glutamine, tyrosine, serine, cysteine, threonine, alanine, β-alanine, proline, tryptophan, methionine, phenylalanine, valine, leucine, and isoleucine, and the above organic acid may include one or more of adipic acid, oxalic acid, tartaric acid, fumaric acid, citric acid, mercaptosuccinic acid, glycolic acid, lactic acid, phthalic acid, ascorbic acid, malic acid, maleic acid, malic acid, propionic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), pentetic acid, egtazitic acid, and salts thereof.

[0032] Meanwhile, the content of the chelating agent may be 0.01% to 5% by weight relative to the total weight of the polishing slurry composition.

[0033] The above pH adjuster may comprise at least one acidic substance selected from the group consisting of hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, bromic acid, iodic acid, formic acid, malonic acid, maleic acid, oxalic acid, acetic acid, adipic acid, citric acid, acetic acid, propionic acid, fumaric acid, lactic acid, salicylic acid, pimelic acid, benzoic acid, succinic acid, phthalic acid, butyric acid, glutaric acid, glutamic acid, glycolic acid, lactic acid, aspartic acid, tartaric acid, and salts thereof; and at least one basic substance selected from the group consisting of ammonia, ammonium methylpropanol (AMP), tetramethylammonium hydroxide (TMAH), ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium bicarbonate, sodium carbonate, and imidazole.

[0034] The content of the above pH adjuster may be 0.01% to 5% by weight relative to the total weight of the polishing slurry composition.

[0035] Meanwhile, the pH of the polishing slurry composition according to one embodiment may be 6 to 9. Effects of the invention

[0037] A composite particle for polishing a metal film according to one embodiment is characterized by comprising inorganic particles whose surface is surface-modified with alkyne groups and / or alkyl chloride groups. The composite particle reacts with a compound containing alkyne groups and / or a compound containing azide groups in a polishing slurry composition by heat generated during the polishing process, thereby synthesizing an azole compound on the surface of the composite particle, which can inhibit corrosion of the metal film. Accordingly, a polishing slurry composition containing the composite particle for polishing a metal film according to one embodiment can easily control the corrosion level without the addition of additional corrosion inhibitors, achieve an effective corrosion inhibition effect on the metal film, and exhibit excellent polishing rates and physical properties after polishing.

[0039] The effects of the 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 as described in the detailed description of the invention or the claims. Specific details for implementing the invention

[0041] The embodiments are described in detail below. The terms used in the embodiments are for illustrative purposes only and should not be interpreted as being limiting. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as "comprising" or "having" are intended to indicate the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0042] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the embodiments pertain. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in this application.

[0043] In addition, when describing the embodiments, if it is determined that a detailed description of related prior art could unnecessarily obscure the essence of the embodiments, such detailed description is omitted.

[0044] Additionally, terms such as first, second, A, B, (a), (b), etc., may be used when describing the components of the embodiments. These terms are intended merely to distinguish the components from other components, and the nature, order, or sequence of the components is not limited by these terms. Where it is stated that a component is "connected," "combined," or "joined" to another component, it should be understood that the component may be directly connected or joined to the other component, but that another component may also be "connected," "combined," or "joined" between each component.

[0045] Components included in any one embodiment and components having common functions shall be described using the same names in other embodiments. Unless otherwise stated, the descriptions given in any one embodiment may also apply to other embodiments, and specific descriptions shall be omitted to the extent of overlap.

[0046] It is understood that the term “about” refers to a range of numbers that a person skilled in the art would consider equivalent to the stated value in terms of achieving the same function or result. When the term “about” is used with a number or value, the term “about” refers to ±20% of the number or value, primarily ±10% of the number or value, often ±5% of the number or value, or ±2% of the number or value. In some modalities, the term “about” may refer to the number or value itself.

[0047] In this document, each of the phrases such as "A or B", "at least one of A and B", "at least one of A or B", "A, B or C", "at least one of A, B and C", and "at least one of A, B, or C" may include any one of the items listed together in the corresponding phrase, or all possible combinations thereof.

[0049] [Composite particles for polishing metal films]

[0050] A composite particle for polishing a metal film according to one embodiment may include an inorganic particle, and the surface of the inorganic particle may be modified to one or more of a silane compound containing an alkyne group and a silane compound containing an alkyl chloride group.

[0051] The above inorganic particles may comprise one or more of metal oxides and metal oxides in a colloidal state, and specifically, the metal oxides may comprise one or more of, for example, silica, ceria, zirconia, alumina, titania, barium titania, germania, mangania, and magnesia, among which, preferably silica may be included.

[0052] The average diameter of the inorganic particles may be 5 nm to 300 nm, and more specifically, 10 nm to 150 nm. If the average diameter of the inorganic particles is smaller than the lower limit, a decrease in dispersibility and a decrease in polishing rate may occur due to the aggregation of inorganic particles, and issues such as defects may occur due to residual particles after polishing. On the other hand, if the average diameter of the inorganic particles is larger than the upper limit, issues such as scratches may occur.

[0053] In addition, the pore volume of the above inorganic particle is 0.01 cm 3 / g to 1.0cm 3 It can be / g.

[0054] The surface of such inorganic particles can be modified with a silane compound, and the silane compound can be selected from silane compounds containing alkyne groups and / or silane compounds containing alkyl chloride groups.

[0055] The above silane compound containing an alkyne group is a compound that simultaneously contains an alkyne group and a silane group within the compound, and specifically, as an example, may correspond to the compound of Chemical Formula 1 below.

[0056] [Chemical Formula 1]

[0057]

[0059] In the above chemical formula 1, R1 is an alkyl group having 1 to 120 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aromatic ring group having 6 to 20 carbon atoms, which is substituted or unsubstituted with one or more substituents selected from the group consisting of OH, NH2, F, Cl, Br, I, methoxy groups, ethoxy groups, and acetyl groups, while containing Si in the structure.

[0060] Alternatively, to explain specifically using chemical formula names, 3-(Trimethoxysilyl)propylalkyne, 3-(Trimethoxysilyl)propyl-1-phenylalkyne, 3-(Trimethoxysilyl)propyl-1-phenyl-1-hexane, 3-(Trimethoxysilyl)propyl-1-phenyl-1-hexyne, 3-(Trimethoxysilyl)propyl-1-cyclohexylalkyne, 3-(Trimethoxysilyl)propyl-1-bromoalkyne, and 3-(Trimethoxysilyl)propyl-1-pentane (3-(Trimethoxysilyl)propyl-1-pentyne), 3-(Trimethoxysilyl)propyl-1-heptyne), 3-(Trimethoxysilyl)propyl-1-octyne), 3-(Trimethoxysilyl)propyl-1-nonyne), 3-(Trimethoxysilyl)propyl-1-decyne), 3-(Trimethoxysilyl)propyl-4-octyne), 3-(Trimethoxysilyl)propyl-3-hexane It may include, but is not limited to, 3-(Trimethoxysilyl)propyl-3-heptyne, 3-(Trimethoxysilyl)propyl-3-heptyne, 3-(Trimethoxysilyl)propyl-2-octyne and / or 3-(Trimethoxysilyl)propyl-2-heptyne.

[0061] The above silane compound containing an alkyl chloride group is a compound that simultaneously contains an alkyl chloride group and a silane group within the compound, specifically, as an example, trimethylchlorosilane (TMCS), triethylchlorosilane (TECS), triphenylchlorosilane (TPClS), trichloro(methyl)silane (Trichloromethylsilane, TCMS), trichlorobutylsilane (Trichlorobutylsilane), trichloroacetylsilane (TCAS), trichloropropylsilane (TCPS), trichloromethyl ether silane (TCMES), trichlorobenzylsilane (TCBS), trichloromethylamine silane (TCMA), and trichlorophenylsilane (TCPSSi). It may include, but is not limited to, trichlorobutylmethylsilane (TCBMS), trichlorohexylsilane (TCHS), trichloroisobutylsilane (TCIBS), and / or trichloromethylbenzylsilane (TCMBS).

[0062] A composite particle for polishing a metal film according to one embodiment may have its surface modified with one or more of the silane compounds containing alkyne groups and silane compounds containing alkyl chloride groups listed above, so that the alkyne groups and alkyl chloride groups are bonded to the surface of the composite particle for polishing a metal film.

[0064] The above alkyne group or alkyl chloride group reacts with a compound containing an alkyne group and / or a compound containing an azide group, which is a corrosion inhibitor of the polishing slurry composition described later, to form an azole group.

[0065] Azole compounds, which are compounds containing azole groups, reduce the elution rate of metal ions and thereby suppress the occurrence of defects such as dishing and corrosion during the polishing process; thus, the composite particles for polishing metal films according to one embodiment can be used for polishing to suppress dishing and corrosion.

[0067] [Abrasive Slurry Composition]

[0068] A polishing slurry composition according to one embodiment may include composite particles for polishing metal films and a corrosion inhibitor.

[0069] Here, since the composite particles for polishing metal films described above are substantially identical to the composite particles for polishing metal films described in detail above, redundant content will be omitted below.

[0070] The above corrosion inhibitor may include one or more of a compound containing an alkyne group and a compound containing an azide group.

[0071] The above-mentioned compound containing an alkyne group is not significantly limited in type as long as it is a compound containing an alkyne group, but specifically, as an example, it may correspond to a compound represented by the following chemical formula 2.

[0072] [Chemical Formula 2]

[0073]

[0074] In the above chemical formula 2, R1 is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aromatic ring group having 6 to 20 carbon atoms, which is substituted or unsubstituted with one or more substituents selected from the group consisting of OH, NH2, F, Cl, Br, I, methoxy group, ethoxy group, and acetyl group.

[0075] Or, specifically described by chemical formula names, it may include acetylene, phenylacetylene, trimethylsilylacetylene, 1-octadecylacetylene, 1-hexadecylacetylene, 2-acetylhexadiene, 4-octadecene, tributylacetylene, 1-butylacetylene, 1-propylacetylene, 2-methoxy-1-hex-1-phosphine, 1-methyl-1-hex-1-phosphine, 1,4-dimethoxy-2-butylacetylene, vinylacetylene and / or 1,3-dipentylacetylene, etc.

[0076] Meanwhile, the above-mentioned compound containing an azide group is not significantly limited in type as long as it contains an azide group within the compound, but specifically, as an example, it may correspond to a compound represented by the following chemical formula 3.

[0077] [Chemical Formula 3]

[0078]

[0079] In the above chemical formula 3, R2 is a carbon 1 to 10 alkyl group, a carbon 6 to 10 aromatic ring group, or a carbon 3 to 10 cycloalkyl group that is substituted or unsubstituted with one or more substituents selected from the group consisting of OH, NH2, F, Cl, Br, I, methoxy group, ethoxy group, and acetyl group.

[0080] Or, specifically described by chemical name, it may include benzyl azide, ethyl azide, methyl azide, 4-methoxybenzyl azide, 2-chlorobenzyl azide, 3-bromobenzyl azide, N-methyl azide, N-butyl azide, benzoyl azide, 2-hydroxybenzyl azide, 4-aminophenyl azide, 3-methoxybenzyl azide, 4-chlorobenzyl azide, 4-acetylphenyl azide and / or phenylenediamine azide, etc.

[0082] A corrosion inhibitor comprising one or more of the above-mentioned compounds containing alkyne groups and compounds containing azide groups may react with alkyne groups or alkyl chloride groups bonded to the surface of the composite particles for polishing metal films described in detail above, and may be formed as shown in reaction scheme 1 or 2 below as an example.

[0083] [Reaction Equation 1]

[0084]

[0085] [Reaction Equation 2]

[0086]

[0088] Specifically, the composite particles for polishing metal films according to one embodiment may form an azole compound on their surface during the CMP process, based on reaction scheme 3 as an example.

[0089] [Reaction Equation 3]

[0090]

[0092] Meanwhile, a polishing slurry composition according to one embodiment may include 0.01% to 20% by weight of composite particles for polishing a metal film relative to the total weight of the polishing slurry composition, preferably 0.1% to 10% by weight, more preferably 0.5% to 5% by weight. If the content of the composite particles for polishing a metal film is below the lower limit, a problem of reduced polishing speed may occur, and if it exceeds the upper limit, the number of composite particles remaining on the surface of the film to be polished may increase due to the increase in the content of composite particles, and defects such as scratches, dishing, and / or erosion may occur in the pattern of the film to be polished due to over-polishing.

[0094] A polishing slurry composition according to one embodiment may further include one or more of an oxidizing agent, a chelating agent, and a pH adjuster.

[0095] The above oxidizing agent may be used to improve the polishing speed by inducing oxidation of the film to be polished, and specific types include hydrogen peroxide, urea, hydrogen peroxide, urea, percarbonate, periodic acid, periodate, perchloric acid, perchlorate, perbromic acid, perbrodate, perboric acid, perborate, potassium permanganate, sodium perborate, permanganic acid, permanganate, persulfate, bromate, chlorite, chlorate, chromate, dichromate, iodate, iodic acid, ammonium persulfate, benzoyl peroxide, calcium peroxide, barium peroxide, sodium peroxide, dioxygenyl, ozone, ozonide. It may include one or more of nitrate, hypochlorite, hypohalite, chromium trioxide, pyridinium chlorochromate, nitrous oxide, monopersulfate, dipersulfate, and sodium peroxide.

[0096] The above-mentioned chelating agent is used as a type of polishing accelerator and plays a role in increasing the polishing speed through a chemical reaction that forms a complex compound with metal atoms of the metal film to be polished. Specific types may include one or more of amino acids and organic acids.

[0097] Here, the amino acid may include, as an example, one or more of glycine, arginine, lysine, histidine, aspartic acid, glutamic acid, asparagine, glutamine, tyrosine, serine, cysteine, threonine, alanine, β-alanine, proline, tryptophan, methionine, phenylalanine, valine, leucine, and isoleucine, and the organic acid may include one or more of adipic acid, oxalic acid, tartaric acid, fumaric acid, citric acid, mercaptosuccinic acid, glycolic acid, lactic acid, phthalic acid, ascorbic acid, malic acid, maleic acid, malic acid, propionic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), pentetic acid, egtazitic acid, and salts thereof.

[0098] In addition, the chelating agent may be included in an amount of 0.01% to 5% by weight relative to the total weight of the polishing slurry composition, and more specifically, in an amount of 0.1% to 3% by weight.

[0099] The above pH adjuster is intended to provide an optimal pH to further enhance the effects of improving polishing speed and surface quality, and may include one or more of acidic and basic substances.

[0100] Here, the acidic substance may include, as an example, at least one selected from the group consisting of hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, bromic acid, iodic acid, formic acid, malonic acid, maleic acid, oxalic acid, acetic acid, adipic acid, citric acid, acetic acid, propionic acid, fumaric acid, lactic acid, salicylic acid, pimelic acid, benzoic acid, succinic acid, phthalic acid, butyric acid, glutaric acid, glutamic acid, glycolic acid, lactic acid, aspartic acid, tartaric acid, and salts thereof, and the basic substance may include at least one selected from the group consisting of ammonia, ammonium methylpropanol (AMP), tetramethylammonium hydroxide (TMAH), ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium bicarbonate, sodium carbonate, and imidazole.

[0101] In addition, the pH adjuster may be included in an amount of 0.01% to 5% by weight relative to the total weight of the polishing slurry composition, and more specifically, in an amount of 0.1% to 3% by weight.

[0103] In one embodiment, the polishing slurry composition may contain an appropriate amount of the pH adjuster described above, so that the pH of the polishing slurry composition may be 6 to 9, and preferably 7 to 8.

[0104] If the pH of the polishing slurry composition is below the lower limit or exceeds the upper limit, the inherent role and effect of the components constituting the polishing slurry composition may be reduced due to changes in the composition of the polishing slurry composition and the charge state of the film to be polished. In particular, if the pH of the composition exceeds the upper limit, the polishing speed may decrease due to damage to the silica of the polishing particles, etc., and if the pH of the composition is below the lower limit, the chelating agent [is a proton (H + The polishing speed may decrease as the metal ion chelating ability decreases due to combination with ), etc.

[0106] [Grinding Target]

[0107] A polishing slurry composition according to one embodiment can be used for polishing a metal film.

[0108] The metal film is substantially the same as the metal film described in detail above in the composite particles for polishing metal films, and specifically, the film to be polished may be a metal film comprising one or more of a metal, a metal nitride, a metal oxide, and a metal alloy.

[0109] The metal in the above metal, metal nitride, metal oxide, and metal alloy may include one or more of copper (Cu), tungsten (W), molybdenum (Mo), indium (In), tin (Sn), silicon (Si), titanium (Ti), vanadium (V), gadollium (Ga), manganese (Mn), iron (Fe), cobalt (Co), zinc (Zn), zirconium (Zr), hafnium (Hf), aluminum (Al), niobium (Nb), nickel (Ni), chromium (Cr), tantalum (Ta), and ruthenium (Ru). More specifically, it may include copper.

[0111] In addition, according to one embodiment, a method for chemical mechanical polishing (CMP) of a wafer for a semiconductor device can be provided using the polishing slurry composition.

[0113] The invention will be described in detail below with reference to the following examples and comparative examples. However, the technical scope of the invention is not limited or restricted by such examples.

[0115] Preparation Examples 1 to 3: Preparation of surface-modified composite particles for polishing metal films

[0116] Colloidal silica surface-modified with a surface-modifying compound according to Table 1 below was obtained by adding a modifier to an aqueous dispersion at pH 0 and stirring at 45°C for 4 hours.

[0118] Surface modification compound Preparation Example 1 3-(Trimethoxysilyl)propylalkyne Preparation Example 2 3-(Trimethoxysilyl)propyl-1-cyclohexylalkyne Preparation Example 3 (3-(Trimethoxylsilyl)propyl-1-phenylalkyne)

[0120] Examples 1 to 7: Preparation of polishing slurry compositions

[0121] A polishing slurry composition according to the composition of Table 2 below was prepared using the composite particles prepared in Preparation Examples 1 to 3 above.

[0123] Comparative Examples 1 to 4: Preparation of polishing slurry compositions

[0124] A polishing slurry composition was prepared in the same manner as in the above example, according to the composition of Table 2 below, using surface-unmodified colloidal silica as abrasive particles.

[0126] Abrasive particles Abrasive particles Content pH Corrosion inhibitor Chelating agent Oxidizing agent Example 1 Composite particles of Preparation Example 1 1.0wt% 7 Acetylene 0.2wt% 1.5wt% 1.0wt% Example 2 Composite particles of Preparation Example 2 1.0wt% 7 1-Hexadecyl acetylene 0.2wt% 1.5wt% 1.0wt% Example 3 Composite particles of Preparation Example 3 1.0wt% 7 Tributyl acetylene 0.2wt% 1.5wt% 1.0wt% Example 4 Composite particles of Preparation Example 1 1.0wt% 7 1-Propylacetylene 0.2wt% 1.5wt% 1.0wt% Example 5 Composite particles of Preparation Example 2 1.0wt% 7 2-Acetylhexadiene 0.2wt% 1.5wt% 1.0wt% Example 6 Composite particles of Preparation Example 3 1.0wt% 7 1-Butylacetylene 0.2wt% 1.5wt% 1.0wt% Example 7 Composite particles of Preparation Example 1 1.0wt% 7 Vinyl acetylene 0.2wt% 1.5wt% 1.0wt% Comparative Example 1 colloidal silica 1.0wt% 7 1,4-Dimethyl-1,2,4-Triazole 0.2wt% 1.5wt% 1.0wt% Comparative Example 2 colloidal silica 1.0wt% 7 1-Tolyl-4-butyl-1,2,4-Triazole 0.2wt% 1.5wt% 1.0wt% Comparative Example 3 colloidal silica 1.0wt% 7 1-Phenyl-3-Octyl-1,2,4-Triazole 0.2wt% 1.5wt% 1.0wt% Comparative Example 4 colloidal silica 1.0wt% 7 - 1.5wt% 1.0wt%

[0128] Experimental Example: Evaluation of Polishing Characteristics

[0129] Polishing of a copper pattern wafer was performed using the polishing slurry compositions of the examples and comparative examples under the following polishing conditions.

[0130] [Grinding Conditions]

[0131] (1) Grinding equipment: SP-03 / K1000 (KCT Co.)

[0132] (2) Carrier rpm : 98

[0133] (3) Platen rpm : 87

[0134] (4) Wafer Pressure: 3 psi

[0135] (5) Slurry Flow rate (ml / min): 250 ml / min

[0136] (6) Pad: IC 1000

[0138] After polishing a copper pattern wafer using the polishing slurry compositions according to the examples and comparative examples, the polishing speed and defects on the wafer surface after polishing were measured. The results are shown in Table 3 below.

[0140] Cu polishing rate (Å / min) Surface condition after polishing Example 1 8,352 ◎ Example 2 7,783 ◎ Example 3 11,674 ◎ Example 4 13,171 ○ Example 5 9,316 ◎ Example 6 9,552 ◎ Example 7 12,764 ○ Comparative Example 1 6,871 △ Comparative Example 2 7,555 △ Comparative Example 3 8,127 △ Comparative Example 4 17,136 ×

[0142] Surface condition after polishing

[0143] ◎ : Excellent surface condition after polishing

[0144] ○ : Excellent surface condition after polishing

[0145] △ : Poor surface condition after polishing

[0146] × : Very poor surface condition after polishing

[0148] As can be seen in Table 3 above, when polishing was performed using Examples 1 to 7, which are polishing slurry compositions according to one embodiment, the polishing rate was superior, and surface defects were also significantly less compared to Comparative Examples 1 to 4.

[0150] Although the embodiments have been described as limited, those skilled in the art can apply various technical modifications and variations based on the above. For example, appropriate results can be achieved even if the described techniques are performed in a different order than described, and / or the components of the described system, structure, device, circuit, etc. are combined or assembled in a form different from described, or replaced or substituted by other components or equivalents.

[0151] Therefore, other implementations, other embodiments, and equivalents to the claims also fall within the scope of the claims set forth below.

Claims

Claim 1 A composite particle for polishing a metal film, comprising inorganic particles, wherein the surface of the inorganic particles is modified by one or more of a silane compound containing an alkyne group and a silane compound containing an alkyl chloride group. Claim 2 A composite particle for polishing a metal film according to claim 1, wherein the inorganic particle comprises one or more of a metal oxide and a metal oxide in a colloidal state, and the metal oxide comprises one or more of silica, ceria, zirconia, alumina, titania, barium titania, germania, mangania, and magnesia. Claim 3 A composite particle for polishing a metal film according to claim 1, wherein the average diameter of the inorganic particle is 5 nm to 300 nm. Claim 4 In claim 1, the silane compound containing the alkyne group is 3-(trimethoxysilyl)propylalkyne, 3-(trimethoxysilyl)propyl-1-phenylalkyne, 3-(trimethoxysilyl)propyl-1-phenyl-1-hexane, 3-(trimethoxysilyl)propyl-1-phenyl-1-hexyne, 3-(trimethoxysilyl)propyl-1-cyclohexylalkyne, 3-(trimethoxysilyl)propyl-1-bromoalkyne, and 3-(trimethoxysilyl)propyl-1-pentane (3-(Trimethoxysilyl)propyl-1-pentyne), 3-(Trimethoxysilyl)propyl-1-heptyne), 3-(Trimethoxysilyl)propyl-1-octyne), 3-(Trimethoxysilyl)propyl-1-nonyne), 3-(Trimethoxysilyl)propyl-1-decyne), 3-(Trimethoxysilyl)propyl-4-octyne), 3-(Trimethoxysilyl)propyl-3-hexane Composite particles for polishing metal films comprising one or more of (3-(Trimethoxysilyl)propyl-3-heptyne), 3-(Trimethoxysilyl)propyl-3-heptyne, 3-(Trimethoxysilyl)propyl-2-octyne, and 3-(Trimethoxysilyl)propyl-2-heptyne. Claim 5 In claim 1, the silane compound comprising the alkyl chloride group is trimethylchlorosilane (TMCS), triethylchlorosilane (TECS), triphenylchlorosilane (TPClS), trichloro(methyl)silane (Trichloromethylsilane, TCMS), trichlorobutylsilane, trichloroacetylsilane (TCAS), trichloropropylsilane (TCPS), trichloromethylethersilane (TCMES), trichlorobenzylsilane (TCBS), trichloromethylaminesilane (TCMA), trichlorophenylsilane (TCPSSi), trichlorobutylmethylsilane, Composite particles for polishing metal films, comprising one or more of TCBMS), trichlorohexylsilane (TCHS), trichloroisobutylsilane (TCIBs), and trichloromethylbenzylsilane (TCMBS). Claim 6 A composite particle for polishing a metal film according to claim 1, wherein the metal film comprises one or more of a metal, a metal nitride, a metal oxide, and a metal alloy, and the metal of the metal, metal nitride, metal oxide, and metal alloy comprises one or more of copper (Cu), tungsten (W), molybdenum (Mo), indium (In), tin (Sn), silicon (Si), titanium (Ti), vanadium (V), gadollium (Ga), manganese (Mn), iron (Fe), cobalt (Co), zinc (Zn), zirconium (Zr), hafnium (Hf), aluminum (Al), niobium (Nb), nickel (Ni), chromium (Cr), tantalum (Ta), and ruthenium (Ru). Claim 7 A polishing slurry composition comprising: composite particles for polishing a metal film as described in claim 1; and a corrosion inhibitor, wherein the corrosion inhibitor comprises one or more of a compound containing an alkyne group and a compound containing an azide group. Claim 8 A polishing slurry composition according to claim 7, wherein the compound containing the alkyne group comprises one or more of acetylene, phenylacetylene, trimethylsilylacetylene, 1-octadecylacetylene, 1-hexadecylacetylene, 2-acetylhexadiene, 4-octadecene, tributylacetylene, 1-butylacetylene, 1-propylacetylene, 2-methoxy-1-hex-1-phosphine, 1-methyl-1-hex-1-phosphine, 1,4-dimethoxy-2-butylacetylene, vinylacetylene, and 1,3-dipentylacetylene. Claim 9 A polishing slurry composition according to claim 7, wherein the compound containing the azide group comprises one or more of benzyl azide, ethyl azide, methyl azide, 4-methoxybenzyl azide, 2-chlorobenzyl azide, 3-bromobenzyl azide, N-methyl azide, N-butyl azide, benzoyl azide, 2-hydroxybenzyl azide, 4-aminophenyl azide, 3-methoxybenzyl azide, 4-chlorobenzyl azide, 4-acetylphenyl azide, and phenylenediamine azide. Claim 10 In claim 7, the metal film polishing composite particles are included in the polishing slurry composition at a concentration of 0.01% to 20% by weight. Claim 11 In claim 7, the polishing slurry composition further comprises one or more of an oxidizing agent, a chelating agent, and a pH adjuster. Claim 12 In claim 11, the oxidizing agent is hydrogen peroxide, urea, hydrogen peroxide, urea, percarbonate, periodic acid, periodate, perchloric acid, perchlorate, perbromic acid, perbrodate, perboric acid, perborate, potassium permanganate, sodium perborate, permanganic acid, permanganate, persulfate, bromate, chlorite, chlorate, chromate, dichromate, iodate, iodic acid, ammonium persulfate, benzoyl peroxide, calcium peroxide, barium peroxide, sodium peroxide, dioxygenyl, ozone, ozonide, nitrate, A polishing slurry composition comprising one or more of hypochlorite, hypohalite, chromium trioxide, pyridinium chlorochromate, nitrous oxide, monopersulfate, dipersulfate, and sodium peroxide, wherein the content of the oxidizing agent is 0.01% to 5% by weight relative to the total weight of the polishing slurry composition. Claim 13 A polishing slurry composition according to claim 11, wherein the chelating agent comprises one or more of an amino acid and an organic acid, and the content of the chelating agent is 0.01% to 5% by weight relative to the total weight of the polishing slurry composition. Claim 14 A polishing slurry composition according to claim 13, wherein the amino acid comprises one or more of glycine, arginine, lysine, histidine, aspartic acid, glutamic acid, asparagine, glutamine, tyrosine, serine, cysteine, threonine, alanine, β-alanine, proline, tryptophan, methionine, phenylalanine, valine, leucine, and isoleucine, and the organic acid comprises one or more of adipic acid, oxalic acid, tartaric acid, fumaric acid, citric acid, mercaptosuccinic acid, glycolic acid, lactic acid, phthalic acid, ascorbic acid, malic acid, maleic acid, malic acid, propionic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), pentetic acid, egtazitic acid, and salts thereof. Claim 15 In claim 11, the pH adjuster comprises an acidic substance comprising at least one selected from the group consisting of hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, bromic acid, iodic acid, formic acid, malonic acid, maleic acid, oxalic acid, acetic acid, adipic acid, citric acid, acetic acid, propionic acid, fumaric acid, lactic acid, salicylic acid, pimelic acid, benzoic acid, succinic acid, phthalic acid, butyric acid, glutaric acid, glutamic acid, glycolic acid, lactic acid, aspartic acid, tartaric acid, and salts thereof; A polishing slurry composition comprising one or more basic substances selected from the group consisting of ammonia, ammonium methylpropanol (AMP), tetramethylammonium hydroxide (TMAH), ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium bicarbonate, sodium carbonate, and imidazole, wherein the content of the pH adjuster is 0.01% to 5% by weight relative to the total weight of the polishing slurry composition. Claim 16 In claim 7, a polishing slurry composition having a pH of 6 to 9.

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