Slurry composition for polishing, and method for manufacturing integrated circuit element using the same

Abstract

To provide: a slurry composition for polishing; and a method for manufacturing an integrated circuit element using the same.SOLUTION: The slurry composition for polishing includes abrasive particles formed of a cerium-based metal organic framework and water. The cerium-based metal organic framework has a three-dimensional network structure that includes a plurality of cerium hexanuclear nanoclusters each including six cerium atoms, and a plurality of organic linkers each of which is connected between two cerium hexanuclear nanoclusters that are selected from the plurality of cerium hexanuclear nanoclusters. In order that the integrated circuit element is manufactured, the film to be polished is polished by a CMP (chemical mechanical polishing) process, with the use of the slurry composition for polishing.SELECTED DRAWING: Figure 4

Description

[Technical field]

[0001] The present invention relates to a slurry composition and a method for manufacturing an integrated circuit device using the same, and more particularly to a slurry composition for polishing a target film using a chemical mechanical polishing (CMP) process and a method for manufacturing an integrated circuit device using the same. [Background technology]

[0002] Due to the development of electronic technology, the downscaling of integrated circuit devices is progressing rapidly, and the line width and pitch of unit elements included in the integrated circuit devices are also becoming finer. As a result, it is necessary to improve the polishing efficiency of the target film to minimize physical damage to the target film, thereby improving the life and reliability of the integrated circuit devices. Summary of the Invention [Problem to be solved by the invention]

[0003] The technical problem to be solved by the technical concept of the present invention is to provide a polishing slurry composition that can increase the polishing rate of a film to be polished while preventing defects such as scratches or physical damage on the polishing surface of the film to be polished.

[0004] Another technical problem that the technical concept of the present invention aims to solve is to provide a method for manufacturing an integrated circuit device, which can improve the productivity of an integrated circuit device manufacturing process and the reliability of an integrated circuit device by increasing the polishing speed of the film to be polished while preventing defects such as scratches or physical damage on the polishing surface of the film to be polished. [Means for solving the problem]

[0005] A polishing slurry composition according to one aspect of the technical concept of the present invention includes abrasive particles having a cerium-based metal organic framework, and water. The cerium-based metal organic framework has a three-dimensional network structure including a plurality of cerium hexanuclear nanoclusters, each of which includes six cerium atoms, and a plurality of organic linkers, each of which is connected between two cerium hexanuclear nanoclusters selected from the plurality of cerium hexanuclear nanoclusters.

[0006] A polishing slurry composition according to another aspect of the present invention includes abrasive particles having a cerium-based metal organic framework having a three-dimensional network structure, and water, and the cerium-based metal organic framework has a bonding structure represented by the following general formula 1:

[0007] [General formula 1] {[Ce 6 ]-L} n In the general formula 1, [Ce 6 ] is a cerium hexanuclear nanocluster, each of which contains six cerium atoms and a plurality of oxygen atoms; L is an organic linker; n is an integer of 2 or greater.

[0008] In one embodiment of a method for manufacturing an integrated circuit device according to the technical concept of the present invention, a film to be polished is formed on a substrate. The film to be polished is polished by a chemical mechanical polishing (CMP) process using a slurry composition including abrasive particles made of a cerium-based metal organic framework and water. The cerium-based metal organic framework includes a plurality of cerium hexanuclear nanoclusters each including six cerium atoms, and a plurality of organic linkers connected between two cerium hexanuclear nanoclusters selected from the plurality of cerium hexanuclear nanoclusters. Effect of the Invention

[0009] According to the polishing slurry composition according to the technical concept of the present invention, when polishing a film to be polished, defects such as scratches or physical damage can be prevented on the polishing surface of the film to be polished, and the polishing rate of the film to be polished can be increased.

[0010] According to the method for manufacturing an integrated circuit element based on the technical concept of the present invention, by polishing a film to be polished using a polishing slurry composition based on the technical concept of the present invention, it is possible to improve the productivity of the integrated circuit element manufacturing process and provide an integrated circuit element with improved reliability. [Brief description of the drawings]

[0011] [Figure 1] 1 is a partially cutaway perspective view showing a schematic configuration of a polishing apparatus according to an embodiment of the present invention; [Diagram 2] FIG. 1 is a conceptual perspective view of an exemplary cerium-based metal-organic framework included in a slurry composition according to an embodiment of the present invention. [Figure 3A] FIG. 3 is a conceptual perspective view showing a schematic crystal structure of the cerium hexanuclear nanocluster illustrated in FIG. 2. [Figure 3B]2 is an exemplary chemical structure of the organic linkers illustrated in FIG. 1. [Figure 4] 2 is a flowchart illustrating a method for manufacturing an integrated circuit device according to an embodiment of the present invention. [Figure 5A] 1A to 1C are cross-sectional views illustrating a process sequence for explaining a method of manufacturing an integrated circuit device according to an embodiment of the present invention. [Figure 5B] 1A to 1C are cross-sectional views illustrating a process sequence for explaining a method of manufacturing an integrated circuit device according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings. The same reference numerals are used to refer to the same components in the drawings, and duplicated descriptions thereof will be omitted.

[0013] FIG. 1 is a partially cutaway perspective view illustrating a schematic configuration of a polishing apparatus according to an embodiment of the present invention.

[0014] 1, a polishing apparatus 1 can be used to polish a surface of a wafer WF using a chemical mechanical polishing (CMP) process. In FIG. 1, a rotary type polishing apparatus 1 is illustrated.

[0015] The polishing apparatus 1 may include a rotating disk-shaped platen 20. The platen 20 may be disposed to be rotatable about a central axis 25 of the platen 20 using a motor 21. For example, the motor 21 may rotate a drive shaft 24 to rotate the platen 20. A polishing pad 10 may be disposed on an upper surface of the platen 20. The polishing pad 10 may include a polishing layer 12 and a support layer 14. The support layer 14 may serve to support the polishing pad 10 so that it is attached to the platen 20.

[0016] The wafer WF also has exposed thereon a film to be polished, which may be, for example, an insulating film, a semiconductor film, a metal film, or an alloy film. The wafer WF may be a structure for forming an integrated circuit device, a structure for forming a TFT-LCD (Thin Film Transistor-Liquid Crystal Display), or a structure including various substrates such as a glass substrate, a ceramic substrate, or a polymer substrate.

[0017] The polishing apparatus 1 may include a slurry port 30 for supplying a slurry composition SC according to an embodiment of the present invention onto the polishing pad 10. The polishing apparatus 1 further includes a polishing pad conditioner 60. The polishing pad conditioner 60 may be configured to perform a dressing process for periodically polishing and planarizing the surface of the polishing pad 10 so that the polishing pad 10 provides a certain polishing efficiency. The term "slurry composition" as used herein refers to a polishing slurry composition used for polishing a film to be polished in a CMP process. In the present specification, the terms "slurry composition" and "polishing slurry composition" may be used interchangeably.

[0018] The polishing apparatus 1 may include at least one carrier head 40. A wafer WF may be loaded onto the carrier head 40. With the wafer WF loaded onto the carrier head 40 positioned to face the platen 20, the carrier head 40 may be configured to rotate while applying pressure to the wafer WF toward the platen 20. Although only one carrier head 40 is illustrated above the polishing pad 10 in FIG. 1, a plurality of carrier heads 40 may be disposed above the polishing pad 10. The carrier head 40 may be configured to control the pressure applied to the wafer WF.

[0019] The carrier head 40 may include a retaining ring 42 necessary to hold the wafer WF. The carrier head 40 may be supported by a support structure 50, such as a carousel or a track, and may be coupled to a carrier head rotation motor 54 through a drive shaft 52 to be rotated about a central axis 55 of the drive shaft 52.

[0020] The polishing apparatus 1 may further include a control system for controlling the rotation of the platen 20. The control system may include a controller 90, such as a general-purpose programmable digital computer, an output device 92, such as a monitor, and an input device 94, such as a keyboard. Although Fig. 1 illustrates a configuration in which the control system is connected only to the motor 21, this is merely an example, and the control system may also be connected to the carrier head 40 to adjust the pressure or rotation speed of the carrier head 40. The control system may also be connected to the slurry port 30 to adjust the supply of the slurry composition SC.

[0021] A slurry composition SC according to an embodiment of the present invention may be used to polish a film to be polished on a wafer WF. The slurry composition SC includes abrasive particles formed of a cerium-based metal organic framework, and water. The cerium-based metal organic framework may have a three-dimensional network structure including a plurality of cerium hexanuclear nanoclusters each including six cerium atoms, and a plurality of organic linkers connected between two cerium hexanuclear nanoclusters selected from the plurality of cerium hexanuclear nanoclusters. As used herein, the term "metal organic framework" refers to a structure in which metal ions and organic substances chemically bonded to each other form a lattice (frame). The chemical bond may be a coordinate bond, a covalent bond, or chemical adsorption.

[0022] The cerium-based metal organic framework has various three-dimensional structures, sizes, volumes, and chemical properties depending on the types of the organic linkers constituting the cerium-based metal organic framework. The cerium-based metal organic framework can form coordinate bonds with the organic linkers through a strong bond between the cerium hexanuclear nanoclusters and oxygen atoms provided by the organic linkers. Therefore, the cerium-based metal organic framework has relatively higher mechanical stability and chemical stability than a typical metal organic framework composed of a divalent metal or a trivalent metal.

[0023] In an exemplary embodiment, the cerium-based metal-organic framework may include a bonding structure represented by General Formula 1 below:

[0024] [General formula 1] {[Ce 6 ]-L} n In the general formula 1, [Ce 6 is a cerium hexanuclear nanocluster, each of which contains six cerium atoms and a plurality of oxygen atoms; L is an organic linker; n is an integer of 2 or greater.

[0025] In an exemplary embodiment, in general formula 1, n is an integer selected from the range of 2 to 300, or from the range of 2 to 600, but is not limited thereto.

[0026] In an exemplary embodiment, the cerium hexanuclear nanocluster has a composition represented by Formula 1:

[0027] [ka] In Chemical Formula 1, x is an integer from 4 to 8; y is an integer from 1 to 8; A includes at least one of a carboxylate, a nitrate, an amino acid salt, and a chloride ion.

[0028] In another exemplary embodiment, the cerium hexanuclear nanocluster has a composition represented by Formula 2:

[0029] [ka] Figure 2 is a schematic perspective view of an exemplary cerium-based metal-organic framework 100 included in a slurry composition SC according to an embodiment of the present invention. Figure 3A is a schematic perspective view showing a schematic crystal structure of a cerium hexanuclear nanocluster 110 illustrated in Figure 2. Figure 3B is an exemplary chemical structure of an organic linker 120 illustrated in Figure 1.

[0030] 2, 3A, and 3B, the cerium-based metal-organic framework 100 may include a plurality of cerium hexanuclear nanoclusters 110 and a plurality of organic linkers 120 connected between two cerium hexanuclear nanoclusters 110 selected from the plurality of cerium hexanuclear nanoclusters 110. Each of the plurality of cerium hexanuclear nanoclusters 110 may include six cerium atoms 112 and a plurality of oxygen atoms 114.

[0031] In an exemplary embodiment, the cerium hexanuclear nanoclusters 110 included in the cerium-based metal-organic framework 100 are each {CeO 8}, {CeO 9}, or a combination thereof, six CeOx (x is 8 or 9) polyhedra are connected to each other via oxo bridges and / or hydroxo bridges to form a polyoxometalate structure. Each of the cerium hexanuclear nanoclusters 110 has a three-dimensional framework structure of polyanions having a polyhedral crystal structure. In an exemplary embodiment, each of the cerium hexanuclear nanoclusters 110 may have an average particle size of about 1 nm to about 2 nm, but is not limited thereto.

[0032] Although the organic linker 120 is benzene-1,4-carboxylate (also referred to as benzene-1,4-dicarboxylic acid, terephthalate) as illustrated in FIG. 2 and FIG. 3B, the technical idea of ​​the present invention is not limited thereto.

[0033] In an exemplary embodiment, the organic linkers 120 constituting the cerium-based metal-organic framework 100 each have anionic functional groups and can be chemically bonded to at least two cerium hexanuclear nanoclusters selected from the cerium hexanuclear nanoclusters 110 through the anionic functional groups. The chemical bond can be a coordinate bond, a covalent bond, or chemical adsorption. For example, the chemical bond can be a coordinate bond, but is not limited thereto.

[0034] In an exemplary embodiment, each of the organic linkers 120 constituting the cerium-based metal-organic framework 100 is also a charged organic linker. The charged organic linker is a carboxylate functional group (-COO - ), Sulfate (SO 3 -Each of the plurality of organic linkers 120 may include at least two charged functional groups. In an exemplary embodiment, each of the plurality of organic linkers 120 may include a bidentate ligand, a tridentate ligand, or a tetradentate ligand. For example, each of the plurality of organic linkers 120 may include two, three, or four carboxylate functional groups (-COO - ).

[0035] In the slurry composition SC according to an embodiment of the present invention, the cerium-based metal-organic framework constituting the abrasive particles has a plurality of organic linkers each of which is a substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 2 -C 20 Alkenyl, substituted or unsubstituted C 2 -C 20 Alkynyl, substituted or unsubstituted C 1 -C 20 Heteroalkyl, substituted or unsubstituted C 2 -C 20 Heteroalkenyl, substituted or unsubstituted C 2 -C 20 Heteroalkynyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, substituted or unsubstituted C 3 -C 20 Cycloalkenyl, or substituted or unsubstituted C 6 -C 30 For example, the organic linkers included in the cerium-based metal-organic framework may include an aromatic ring.

[0036] When at least a portion of the organic linkers has a substituted hydrocarbon group, some or all of the hydrogen atoms contained in the hydrocarbon group contained in the organic linker may be substituted with a substituent. As used herein, the term "substituent" refers to an atom or atomic group substituted at the position of a hydrogen atom in the structure. The substituent may be selected from, but is not limited to, a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, a nitro group, a cyano group, and a thiol group (-SH).

[0037] In an exemplary embodiment, the organic linkers included in the cerium-based metal-organic framework constituting the slurry composition SC may each be a carboxylate derived from an organic compound. For example, the organic linkers may each be benzene-1,4-dicarboxylic acid, 5-bromoisophthalic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 5-cyano-1,3-benzene ... 2,5-diaminoterephthalic acid acid, 5-ethynyl-1,3-benzenedicarboxylic acid, 4,4'-biphenyldicarboxilic 2,6-naphthalenedicarboxylic acid 9,10-anthracenedicarboxylic acid 2,2-diamino-4,4'-stilbenedicarboxylic acid 2,2-dinitro-4,4-stilbenedicarboxylic acid acid, 1,3,5-tricarboxybenzene, biphenyl-3,4',5-tricarboxylic acid acid), 1,3,5-tris(4-carboxyphenyl)benzene, 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine, 1,3,5-tris(4-carboxy[1,1'-biphenyl]-4-yl)benzene, biphenyl-3,3,5,5'-tetracarboxylic acid acid), 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid and 1,1,2,2-tetra(4-carboxylphenyl)ethylene. However, the present invention is not limited to these.

[0038] In an exemplary embodiment, the organic linkers included in the cerium-based metal-organic framework constituting the slurry composition SC may be carboxylates derived from at least one organic compound selected from the following structures:

[0039] [ka] For example, among the organic compounds exemplified above, benzene-1,4-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,3,5-tris(4-carboxyphenyl)benzene may each be present in the cerium-based metal-organic framework in the form of a carboxylate as shown below.

[0040] [ka] In an exemplary embodiment, the size of the cerium-based metal-organic framework constituting the slurry composition SC is about 0.1 μm to about 100 μm, but is not limited thereto.

[0041] The slurry composition SC according to the embodiment of the present invention may further include a dispersant. The dispersant serves to improve the dispersion of the cerium-based metal-organic framework used as abrasive particles in the slurry composition SC. The inclusion of the dispersant in the slurry composition SC may prevent a decrease in the polishing rate in the polishing process using the slurry composition SC, and may improve the dispersibility of the cerium-based metal-organic framework contained in the slurry composition SC, thereby improving the polishing uniformity of the film to be polished.

[0042] In exemplary embodiments, the dispersing agent may comprise at least one material selected from polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl esters, polyoxypropylene ethers, polyoxyethylene methyl ethers, polyethylene glycol sulfonic acid, polyethylene oxide, polypropylene oxide, polyalkyl oxides, polyoxyethylene oxide, polyethylene oxide-propylene oxide copolymers, cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, glycerin, polypropylene glycol, sulfoethyl cellulose, and carboxymethyl sulfoethyl cellulose.

[0043] In an exemplary embodiment, the dispersant may be included in an amount of about 0.01 wt % to about 15 wt %, for example, about 0.05 wt % to about 10 wt %, or about 1 wt % to about 5 wt %, based on the total weight of the slurry composition SC, but is not limited thereto.

[0044] The slurry composition SC according to the embodiment of the present invention may further include a pH adjuster, which adjusts the pH of the slurry composition SC to a desired value.

[0045] In exemplary embodiments, the pH adjuster may comprise, but is not limited to, potassium hydroxide, acetic acid, nitric acid, hydrogen chloride, ammonium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, or combinations thereof.

[0046] In an exemplary embodiment, the slurry composition SC has a pH selected within the range of about 2 to about 11. For example, the slurry composition SC has a pH of about 4 to about 10, or about 5 to about 8. In order to control the pH of the slurry composition SC to a desired value, a suitable amount of the pH adjuster consisting of an acid solution and / or an alkali solution may be used. The pH adjuster is contained in the slurry composition SC in an amount necessary to adjust the polishing slurry composition to a required pH, and the content of the pH adjuster is not particularly limited.

[0047] The slurry composition SC according to the embodiment of the present invention may further include a corrosion inhibitor, which is selectively attached to the layer to be polished and effectively inhibits excessive corrosion of the layer to be polished while maintaining a good polishing rate of the layer to be polished.

[0048] The corrosion inhibitor comprises an azole-containing compound or a water-soluble polymer containing an anionic carboxylic acid. In an exemplary embodiment, the corrosion inhibitor comprises an azole-containing compound, the azole-containing compound comprising a triazole, a tetrazole, a benzotriazole, a tolytriazole, an aminotriazole, an aminobenzimidazole, a pyrazole, an imidazole, an aminotetrazole, or a combination thereof. For example, the corrosion inhibitor may be 5-methyl-1H-benzotriazol, 2,2'-[[(5-methyl-1H-benzotriazole-1-yl)-methyl]imino]bis-ethanol, 1,2,4-triazole, 1,2,3-triazole, 1,2,3-triazolo[4,5-b]pyridine, or a combination thereof.

[0049] When the corrosion inhibitor is contained in the slurry composition CS, the content of the corrosion inhibitor is about 0.001% by weight to about 1% by weight, for example, about 0.001% by weight to about 0.5% by weight.

[0050] The slurry composition SC according to an embodiment of the present invention further includes a polishing booster, which serves to increase the polishing rate of the target layer.

[0051] In an exemplary embodiment, the polishing booster comprises a cationic polymeric salt or an organic acid containing a quaternary ammonium cation. In other exemplary embodiments, the polishing booster comprises arginine, histidine, lysine, aspartic acid, glutamic acid, serine, threonine, asparagine, glutamine, cysteine, selenocysteine, glycine, proline, alanine, valine, leucine, isoleucine, methionine, phenylalanine, tyrosine, tryptophan, a carboxylic acid, or a combination thereof.

[0052] When the polishing booster is made of a polymer, the molecular weight of the polishing booster is about 1,000 to about 1,000,000. The molecular weight is also a weight-averaged molecular weight. If the molecular weight of the polishing booster is too low, the polishing rate may decrease. If the molecular weight of the polishing booster is too high, the dispersibility decreases, making it difficult to perform uniform polishing.

[0053] When the polishing booster is included in the slurry composition CS, the content of the polishing booster is about 0.001 wt % to about 10 wt % based on the total weight of the slurry composition SC.

[0054] The slurry composition SC according to the embodiment of the present invention may further include an organic acid to suppress the polishing rate of the inorganic film. The organic acid may contribute to controlling the polishing rate, the dispersion stability of the slurry composition SC, and the surface characteristics of the film to be polished in the polishing process using the slurry composition SC. The organic acid may be malic acid, citric acid, formic acid, glutaric acid, oxalic acid, phthalic acid, succinic acid, tartaric acid, maleic acid, malonic acid, or a combination thereof.

[0055] When the organic acid is contained in the slurry composition CS, the content of the organic acid is about 0.02 wt % to about 0.1 wt %, or about 0.05 wt % to about 0.1 wt %, based on the total weight of the slurry composition SC.

[0056] The slurry composition CS according to the embodiment of the present invention may further include a biocide, which serves to prevent microbial contamination of the slurry composition CS or the polishing object to which the slurry composition CS is applied.

[0057] In exemplary embodiments, the biocide comprises, but is not limited to, an organo tin compound, a salicylanilide, formaldehyde, a quaternary ammonium compound, 2-bromo-2-nitropropane-1,3-diol (bronopol), 2,2-dibromo-3-nitrilopropionamide (DBNPA), an isothiazolone, a carbamate, a quaternary phosphonium salt (e.g., tetrakis(hydroxymethyl)-phosphonium sulfate (THPS)), sodium chloride, sodium hypochlorite, trichloroisocyanuric acid, dichloroisocyanuric acid, calcium hypochlorite, lithium hypochlorite, chlorine dioxide, ozone, hydrogen peroxide, or a combination thereof.

[0058] When the biocide is included in the slurry composition CS, the content of the biocide is about 0.001% by weight to about 10% by weight based on the total weight of the slurry composition CS. In an exemplary embodiment, the content of the biocide is about 0.001% by weight to about 5% by weight, about 0.001% by weight to about 3% by weight, or about 0.001% by weight to about 1% by weight based on the total weight of the slurry composition CS.

[0059] The content of the abrasive particles made of a cerium-based metal-organic framework in the slurry composition CS is about 0.1 wt % to about 2 wt % based on the total weight of the slurry composition CS, but is not limited thereto.

[0060] The water contained in the slurry composition SC according to the embodiment of the present invention may be deionized water. The content of water contained in the slurry composition SC is not particularly limited, and may be included as the balance together with the main components in the slurry composition SC.

[0061] In an exemplary embodiment, the slurry composition CS according to the embodiment of the present invention can be used to polish various material films. For example, the slurry composition CS can be used to polish silicon-containing films such as silicon oxide films and silicon films.

[0062] A slurry composition SC according to an embodiment of the present invention includes abrasive particles formed of a cerium-based metal-organic framework as abrasive particles, and water. The cerium-based metal-organic framework has a three-dimensional network structure including a plurality of cerium hexanuclear nanoclusters, each of which includes six cerium atoms, and a plurality of organic linkers connected between every two cerium hexanuclear nanoclusters selected from the plurality of cerium hexanuclear nanoclusters.

[0063] In general, when a film to be polished is polished using a conventional slurry composition containing inorganic abrasive particles, the inorganic abrasive particles may damage the polished surface of the film to be polished depending on the polishing conditions. For example, when a film to be polished is polished using a conventional slurry composition containing inorganic abrasive particles, the inorganic abrasive particles may cause the polished surface of the film to be polished to be damaged or contaminated. In addition, the inorganic abrasive particles may shorten the life of a polishing pad used in the polishing process, for example, the polishing pad 10 illustrated in FIG. 1, and cause an increase in the cost of the polishing process.

[0064] As the size of integrated circuit devices, such as memory devices and non-memory devices, becomes smaller, it becomes important to reduce scratch defects when performing a CMP process in the manufacturing process of the integrated circuit devices. As a solution to this problem, attempts have been made to use a relatively soft polishing pad or to use smaller abrasive particles. However, it is difficult for relatively small abrasive particles, such as conventional abrasive particles, to apply a sufficient physical force to the surface of the film to be polished.

[0065] Slurry Composition SC according to an embodiment of the present invention may improve the disadvantages of conventional abrasive particles as described above. Slurry Composition SC according to an embodiment of the present invention may increase the polishing rate of a layer to be polished while preventing defects such as scratches or physical damage on a polishing surface of the layer to be polished by including abrasive particles made of a cerium-based metal-organic framework.

[0066] More specifically, in the slurry composition SC according to the embodiment of the present invention, the cerium hexanuclear nanoclusters included in the abrasive particles made of a cerium-based metal-organic framework have a structure in which six cerium atoms are three-dimensionally bonded together, and have a relatively soft physical property. In addition, the charged cerium hexanuclear nanoclusters can be connected to the organic linkers with a relatively strong bond through chemical bonds with the organic linkers to form a three-dimensional network structure. Therefore, there is no risk of the cerium hexanuclear nanoclusters falling off from the abrasive particles during the CMP process using the slurry composition SC including the abrasive particles made of a cerium-based metal-organic framework. In addition, the cerium-based metal-organic framework has a porous structure in which the cerium hexanuclear nanoclusters and the organic linkers are connected in a three-dimensional network structure, and has a soft physical property. Therefore, even if the abrasive particles made of a cerium-based metal-organic framework are exposed to external shear stress during the CMP process using the slurry composition SC, and some of the cerium hexanuclear nanoclusters may fall off from the abrasive particles, the surface of the abrasive particles may maintain a shape in which the cerium-based metal-organic framework having a three-dimensional network structure is exposed. Therefore, even if a physical change occurs in the abrasive particles due to the shear stress applied to the abrasive particles during the CMP process, it is highly unlikely that the physical change in the abrasive particles will adversely affect the polishing performance or cause scratch defects in the film to be polished.

[0067] In addition, the abrasive particles made of a cerium-based metal organic framework included in the slurry composition SC according to the embodiment of the present invention have a three-dimensional network structure, and can elastically respond to external pressure during the CMP process, and can reduce scratch defects on the surface of the film to be polished by acting as a cushion on the surface of the film to be polished during the CMP process. In addition, the cerium hexanuclear nanoclusters included in the cerium-based metal organic framework have the same or a similar crystal structure as the ceria particles, and can therefore form a relatively strong chemical bond with the film to be polished, e.g., a silicon oxide film, having Si-O bonds during the CMP process, and therefore the cerium hexanuclear nanoclusters included in the cerium-based metal organic framework can interact with the film to be polished through chemical bonds during the CMP process.

[0068] In addition, the cerium-based metal-organic framework that constitutes the abrasive particles has a three-dimensional network structure in which a plurality of cerium hexanuclear nanoclusters are linked to a plurality of organic linkers, and therefore can have a larger particle size than conventional abrasive particles. Therefore, it overcomes the physical force limitations of conventional abrasive particles or abrasive particles consisting only of cerium hexanuclear nanoclusters, interacts relatively strongly with the film to be polished, and increases the polishing rate, and makes it easier to remove the abrasive particles from the surface of the film to be polished in a cleaning process performed after the polishing process is completed.

[0069] As described above, when a layer to be polished is polished using the slurry composition SC according to an embodiment of the present invention, defects such as scratches or physical damage can be prevented from occurring on the polishing surface of the layer to be polished, and the polishing rate of the layer to be polished can be increased, improving the efficiency of the polishing process and contributing to improved productivity in the manufacturing process of integrated circuit devices.

[0070] The abrasive particles made of a cerium-based metal-organic framework contained in the slurry composition SC according to an embodiment of the present invention may be prepared using various synthesis processes well known in the art.

[0071] In an exemplary embodiment, in order to synthesize a cerium-based metal organic framework, a cerium hexanuclear nanocluster may first be synthesized, and then the cerium hexanuclear nanocluster may be reacted with an organic linker precursor to synthesize the cerium-based metal organic framework. In another exemplary embodiment, in order to synthesize a cerium-based metal organic framework, a precursor required for synthesizing a cerium hexanuclear nanocluster and an organic linker precursor may be mixed and reacted together. In this case, the three-dimensional shape of the cerium-based metal organic framework, the method of connecting the cerium-based metal organic framework and the organic linker, the porosity of the cerium-based metal organic framework, etc. may be variously changed depending on the type of the organic linker precursor. Therefore, by appropriately selecting the type of the organic linker precursor as necessary, the three-dimensional shape of the metal organic framework, the method of connecting the cerium-based metal organic framework and the organic linker, the porosity of the cerium-based metal organic framework, etc. may be adjusted.

[0072] In synthesizing a cerium-based metal organic framework, an exemplary synthesis process for synthesizing the cerium-based metal organic framework by first synthesizing a cerium hexanuclear nanocluster and then reacting the cerium hexanuclear nanocluster with an organic linker precursor will be described below.

[0073] First, ammonium cerium (IV) nitrate is mixed with glycine to form cerium hexanuclear nanoclusters, and the cerium hexanuclear nanoclusters are precipitated using a NaCl solution, and the precipitated cerium hexanuclear nanoclusters can be collected. Here, the weight ratio of diammonium cerium nitrate to glycine is 10:2 to 10:3. Then, the cerium hexanuclear nanocluster powder, an organic linker precursor, and a modulator are mixed in a solution of water and DMF (dimethylformamide), and the resulting mixture is aged in an oven maintained at a temperature of 100° C. to synthesize a cerium-based metal organic framework. Here, specific examples of the organic linker precursor are as described above. For example, benzene-1,4-dicarboxylic acid is used as the organic linker precursor. In this case, the weight ratio of the cerium hexanuclear nanocluster powder to benzene-1,4-dicarboxylic acid is also 13:11. The modulator may be, but is not limited to, benzoic acid or acetic acid. The use of the modulator may be omitted.

[0074] As another method for synthesizing a cerium-based metal organic framework, diammonium cerium nitrate and benzene-1,4-dicarboxylic acid are mixed in a molar ratio of 1:1, the resulting mixture is dispersed in a solution in which water and DMF are mixed in a volume ratio of 4:1, a modulator such as benzoic acid or acetic acid is added to the resultant, and the resultant is aged in an oven maintained at a temperature of 100° C., thereby synthesizing a cerium-based metal organic framework. Specific examples of the organic linker precursor are as described above.

[0075] The cerium-based metal-organic framework synthesized as above may be purified, and the cerium-based metal-organic framework may be mixed with water, and an additive such as a pH adjuster may be added thereto, as necessary, to prepare a slurry composition according to the technical concept of the present invention.

[0076] Next, a method for manufacturing an integrated circuit device according to an embodiment of the present invention will be described in detail.

[0077] 4 is a flow chart illustrating a method for manufacturing an integrated circuit device according to an embodiment of the present invention, and FIGs. 5A and 5B are cross-sectional views illustrating a process sequence for illustrating a method for manufacturing an integrated circuit device according to an embodiment of the present invention.

[0078] 4 and 5A, in process P1, a lower structure 220 may be formed on a substrate 210, and a polishing target including a film 230 to be polished may be formed on the lower structure 220. In the process P1, as shown in FIG.

[0079] The substrate 210 may include a semiconductor such as Si or Ge, or a compound semiconductor such as SiGe, SiC, GaAs, InAs, or InP. The substrate 210 may include a conductive region (not shown). The conductive region may include an impurity-doped well, an impurity-doped structure, or a conductive layer.

[0080] The lower structure 220 may include an insulating film such as a silicon oxide film, a silicon nitride film, or a combination thereof. In some other embodiments, the lower structure 220 may include various conductive regions, such as wiring layers, contact plugs, transistors, etc., and insulating patterns that insulate them from each other.

[0081] The film to be polished 230 may be an insulating film, a semiconductor film, a metal film, or an alloy film. In an exemplary embodiment, the film to be polished 230 may be a silicon-containing film having a Si—O bond, such as a silicon oxide film.

[0082] 4 and 5B, in step P2, the target film 230 can be polished by a CMP process using a slurry composition SC according to the technical concept of the present invention. As a result, a planarized film 230P having a reduced thickness compared to the target film 230 is obtained. In order to aid in understanding, the upper surface of the target film 230 illustrated in FIG. 5A is illustrated by a dotted line in FIG. 5B. The detailed composition of the slurry composition SC has been described above.

[0083] 5A according to step P2 of Fig. 4 is also a step of buffing and polishing the film to be polished 230 using a slurry composition SC to remove local steps on the upper surface of the film to be polished 230 or to remove seams on the upper surface of the film to be polished 230. The planarized film 230P obtained as a result of the buffing and polishing process of the film to be polished 230 has a smooth and flat upper surface.

[0084] In an exemplary embodiment, the slurry composition SC used in the step of polishing the film 230 to be polished illustrated in FIG. 5A according to step P2 of FIG. 4 may include abrasive particles having a three-dimensional network structure composed of the cerium-based metal-organic framework 100 described with reference to FIG. 2, and water. The cerium-based metal-organic framework 100 may include a plurality of cerium hexanuclear nanoclusters 110 (see FIG. 3A), each of which includes six cerium atoms, and a plurality of organic linkers connected between two cerium hexanuclear nanoclusters 110 selected from the plurality of cerium hexanuclear nanoclusters 110. Each of the plurality of organic linkers may have a plurality of anionic functional groups and may be chemically bonded to at least two cerium hexanuclear nanoclusters selected from the plurality of cerium hexanuclear nanoclusters 110 through the plurality of anionic functional groups. Each of the plurality of organic linkers may have two, three, or four carboxylate functional groups (-COO -) Specific examples of the organic linkers are as described above. For example, the organic linkers included in the cerium-based metal-organic framework may include an aromatic ring. In an exemplary embodiment, each of the organic linkers is an organic linker 120 illustrated in FIG. 3B.

[0085] In another exemplary embodiment, the slurry composition SC used in the process of polishing the target film 230 illustrated in FIG. 5A according to step P2 of FIG. 4 may include a cerium-based metal-organic framework having a bonding structure represented by General Formula 1 described above.

[0086] In yet another exemplary embodiment, the abrasive particles contained in the slurry composition SC used in the process of polishing the film 230 to be polished illustrated in FIG. 5A according to step P2 of FIG. 4 are composed of a cerium-based metal-organic framework including a plurality of cerium hexanuclear nanoclusters each including six cerium atoms and a plurality of organic linkers connected between two cerium hexanuclear nanoclusters selected from the plurality of cerium hexanuclear nanoclusters, and the cerium-based metal-organic framework has a three-dimensional network structure. In an exemplary embodiment, the plurality of cerium hexanuclear nanoclusters may each include a bonding structure represented by General Formula 1 having a composition represented by Formula 1 or Formula 2 above.

[0087] The slurry composition SC used in the process of polishing the target layer 230 illustrated in FIG. 5A according to the process P2 of FIG. 4 may further include at least one additive selected from a dispersant, a pH adjuster, a corrosion inhibitor, and a polishing booster. Specific configurations and examples of the additives are as described above.

[0088] According to the method for manufacturing an integrated circuit device described with reference to Figures 4, 5A, and 5B, the polishing rate of the film to be polished 230 can be increased while preventing defects such as scratches or physical damage on the polishing surface of the film to be polished 230 by polishing the film to be polished using the slurry composition SC according to the technical concept of the present invention. More specifically, the cerium-based metal-organic framework constituting the polishing particles of the slurry composition SC has a porous structure in which a plurality of cerium hexanuclear nanoclusters and a plurality of organic linkers are connected in a three-dimensional network structure, and has soft physical properties. Therefore, even if the abrasive particles made of the cerium-based metal-organic framework are exposed to external shear stress during polishing of the film to be polished 230 in the CMP process using the slurry composition SC, the abrasive particles can maintain a shape in which the cerium-based metal-organic framework forming a three-dimensional network structure is exposed on the surface of the abrasive particles. Therefore, even if a physical change occurs in the abrasive particles due to the shear stress applied to the abrasive particles during the CMP process, the physical change in the abrasive particles is highly unlikely to adversely affect the polishing performance or to cause scratch defects on the film to be polished. The abrasive particles made of a cerium-based metal-organic framework contained in the slurry composition SC have a three-dimensional network structure and can elastically respond to external pressure during the CMP process and act as a cushion on the surface of the film to be polished during the CMP process, thereby reducing scratch defects on the surface of the film to be polished. Therefore, the productivity of an integrated circuit device manufacturing process using the CMP process using the slurry composition SC can be improved, and an integrated circuit device with improved reliability can be provided.

[0089] Although the present invention has been described in detail above with reference to preferred embodiments, the present invention is not limited to the above embodiments, and various modifications and alterations can be made by those having ordinary skill in the art within the technical spirit and scope of the present invention. [Explanation of symbols]

[0090] 210 Substrate 220 Substructure 230 Film to be polished 230P Flattened film

Claims

1. The polishing agent includes abrasive particles having a cerium-based metal organic framework and water, The cerium-based metal-organic framework has a three-dimensional network structure including a plurality of cerium hexanuclear nanoclusters, each of which includes six cerium atoms, and a plurality of organic linkers, each of which is connected between two cerium hexanuclear nanoclusters selected from the plurality of cerium hexanuclear nanoclusters.

2. The polishing slurry composition of claim 1 , wherein each of the plurality of cerium hexanuclear nanoclusters has a composition represented by Chemical Formula 1. 【Chemistry 1】 In Chemical Formula 1, x is an integer from 4 to 8; y is an integer from 1 to 8; A includes at least one of a carboxylate, a nitrate, an amino acid salt, and a chloride ion.

3. 2. The polishing slurry composition according to claim 1, wherein in the cerium-based metal-organic framework, the organic linkers each have a plurality of anionic functional groups and are chemically bonded to at least two cerium hexanuclear nanoclusters selected from the plurality of cerium hexanuclear nanoclusters via the aforesaid anionic functional groups.

4. In the cerium-based metal-organic framework, the organic linkers are each a substituted or unsubstituted C １ -C ２０ Alkyl, substituted or unsubstituted C ２ -C ２０ Alkenyl, substituted or unsubstituted C ２ -C ２０ Alkynyl, substituted or unsubstituted C １ -C ２０ Heteroalkyl, substituted or unsubstituted C ２ -C ２０ Heteroalkenyl, substituted or unsubstituted C ２ -C ２０ Heteroalkynyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkenyl, or substituted or unsubstituted C ６ -C ３０ 10. The polishing slurry composition of claim 1 comprising an aromatic ring system.

5. In the cerium-based metal organic framework, the organic linkers are benzene-1,4-dicarboxylic acid, 5-bromoisophthalic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 5-cyano-1,3-benzenedicarboxylic acid, and 5-bromoisophthalic acid, respectively. 2,5-diaminoterephthalic acid acid, 5-ethynyl-1,3-benzenedicarboxylic acid, 4,4'-biphenyldicarboxilic 2,6-naphthalenedicarboxylic acid 9,10-anthracenedicarboxylic acid 2,2-diamino-4,4'-stilbenedicarboxylic acid stilbenedicarboxylic acid, 2,2-dinitro-4,4-stilbenedicarboxylic acid, 1,3,5-tricarboxybenzene, biphenyl-3,4',5-tricarboxylic acid acid), 1,3,5-Tris(4-carboxyphenyl)benzene, 2,4,6-Tris(4-carboxyphenyl)-1,3,5-triazine, 1,3,5-tris(4-carboxy[1,1'-biphenyl]-4-yl)benzene, biphenyl-3,3,5,5'-tetracarboxylic acid acid), 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid 2. The polishing slurry composition according to claim 1, comprising a carboxylate obtained from at least one organic compound selected from the group consisting of 1,1,2,2-tetra(4-carboxylphenyl)ethylene, 1,1,2,2-tetra(4-carboxylphenyl)ethylene, and 1,1,2,2-tetra(4-carboxylphenyl)ethylene.

6. The polishing slurry composition of claim 1 further comprising a dispersant.

7. The polishing slurry composition of claim 1 , further comprising a pH adjuster.

8. 10. The polishing slurry composition of claim 1, further comprising at least one selected from a corrosion inhibitor and a polishing booster.

9. 2. The polishing slurry composition of claim 1, wherein the content of the abrasive particles is 0.1 to 2 wt % based on the total weight of the polishing slurry composition.

10. The method includes abrasive particles having a cerium-based metal organic framework having a three-dimensional network structure, and water, The cerium-based metal-organic framework has a bonding structure represented by the following general formula 1: [General formula 1] {[Ce ６ ]-L} ｎ In general formula 1, [Ce ６ ] is a cerium hexanuclear nanocluster, each of which contains six cerium atoms and a number of oxygen atoms; L is an organic linker; n is an integer of 2 or more.

11. In the cerium-based metal organic framework, the organic linker is preferably a substituted or unsubstituted C １ -C ２０ Alkyl, substituted or unsubstituted C ２ -C ２０ Alkenyl, substituted or unsubstituted C ２ -C ２０ Alkynyl, substituted or unsubstituted C １ -C ２０ Heteroalkyl, substituted or unsubstituted C ２ -C ２０ Heteroalkenyl, substituted or unsubstituted C ２ -C ２０ Heteroalkynyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkenyl, or substituted or unsubstituted C ６ -C ３０ 11. The polishing slurry composition of claim 10 comprising an aromatic ring system.

12. 11. The polishing slurry composition of claim 10, wherein in the cerium-based metal-organic framework, the organic linker comprises an aromatic ring.

13. The polishing slurry composition according to claim 10, further comprising at least one selected from the group consisting of a dispersant, a pH adjuster, a corrosion inhibitor, and a polishing booster.

14. forming a film to be polished on a substrate; and polishing the target film by a chemical mechanical polishing (CMP) process using a slurry composition including abrasive particles made of a cerium-based metal organic framework and water, The cerium-based metal-organic framework has a three-dimensional network structure including a plurality of cerium hexanuclear nanoclusters, each of which includes six cerium atoms, and a plurality of organic linkers, each of which is connected between two cerium hexanuclear nanoclusters selected from the plurality of cerium hexanuclear nanoclusters.

15. The method of claim 14, wherein the cerium-based metal-organic framework has a bond structure represented by the following Formula 1: [General formula 1] {[Ce ６ ]-L} ｎ In General Formula 1, [Ce ６ ] is a cerium hexanuclear nanocluster, each of which contains six cerium atoms and a number of oxygen atoms; L is an organic linker; n is an integer of 2 or more.

16. 15. The method of claim 14, wherein in the cerium-based metal-organic framework, the organic linkers each have a plurality of anionic functional groups and are chemically bonded to at least two cerium hexanuclear nanoclusters selected from the plurality of cerium hexanuclear nanoclusters via the aforesaid anionic functional groups.

17. In the cerium-based metal-organic framework, the organic linkers are each a substituted or unsubstituted C １ -C ２０ Alkyl, substituted or unsubstituted C ２ -C ２０ Alkenyl, substituted or unsubstituted C ２ -C ２０ Alkynyl, substituted or unsubstituted C １ -C ２０ Heteroalkyl, substituted or unsubstituted C ２ -C ２０ Heteroalkenyl, substituted or unsubstituted C ２ -C ２０ Heteroalkynyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkenyl, or substituted or unsubstituted C ６ -C ３０ A method for producing an integrated circuit device according to claim 14 comprising an aromatic ring system.

18. In the cerium-based metal organic framework, the organic linkers are benzene-1,4-dicarboxylic acid, 5-bromoisophthalic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 5-cyano-1,3-benzenedicarboxylic acid, and 5-bromoisophthalic acid, respectively. 2,5-diaminoterephthalic acid acid, 5-ethynyl-1,3-benzenedicarboxylic acid, 4,4'-biphenyldicarboxilic 2,6-naphthalenedicarboxylic acid 9,10-anthracenedicarboxylic acid 2,2-diamino-4,4'-stilbenedicarboxylic acid stilbenedicarboxylic acid, 2,2-dinitro-4,4-stilbenedicarboxylic acid, 1,3,5-tricarboxybenzene, biphenyl-3,4',5-tricarboxylic acid acid), 1,3,5-Tris(4-carboxyphenyl)benzene, 2,4,6-Tris(4-carboxyphenyl)-1,3,5-triazine, 1,3,5-tris(4-carboxy[1,1'-biphenyl]-4-yl)benzene, biphenyl-3,3,5,5'-tetracarboxylic acid acid), 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid 15. The method of claim 14, wherein the carboxylate is derived from at least one organic compound selected from the group consisting of 1,1,2,2-tetra(4-carboxylphenyl)ethylene, 1,1,2,2-tetra(4-carboxylphenyl)ethylene, and 1,1,2,2-tetra(4-carboxylphenyl)ethylene.

19. 15. The method of claim 14, wherein the slurry composition further comprises at least one selected from the group consisting of a dispersant, a pH adjuster, a corrosion inhibitor, and a polishing booster.

20. The method of claim 14 , wherein the film to be polished comprises a silicon-containing film.

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