Diazo compounds, chemical mechanical polishing slurry compositions and polishing methods

Abstract

A diazo compound of Formula 1 or a salt thereof, a chemical mechanical polishing slurry composition comprising the compound, and a polishing method using the chemical mechanical polishing slurry composition are disclosed.

Description

[0001] Cross-reference of related applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2022-0007624, filed on January 19, 2022, with the Korean Intellectual Property Office, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] This invention relates to a diazo compound, a chemical mechanical polishing (CMP) slurry composition comprising the diazo compound, and a polishing method using the CMP slurry composition. More specifically, this invention relates to a diazo compound capable of improving polishing smoothness and increasing polishing rate by reducing erosion during polishing, a CMP slurry composition comprising the diazo compound, and a polishing method using the CMP slurry composition. Background Technology

[0004] For the polishing process of copper layers used as metal interconnects in semiconductor devices, sufficient polishing rates, better polishing selectivity than barrier metals or dielectrics, suitable polishing smoothness, and low defect rates are required. Specifically, a CMP paste composition is needed that can achieve high smoothness to form fine patterns while reducing interconnect and layer thickness.

[0005] Generally, improved polishing smoothness can be achieved through various methods, such as increasing the amount of corrosion inhibitors, using polymeric film-forming agents, and reducing the size and / or amount of abrasive particles. However, these methods require a trade-off between the polishing rate and reducing dishing by lowering the copper polishing rate. Specifically, triazole or tetraazole compounds are commonly used as corrosion inhibitors. However, while triazole or tetraazole compounds can provide a degree of corrosion protection when used in large quantities, they suffer from relatively low polishing rates. Summary of the Invention

[0006] One aspect of the present invention is to provide a diazo compound that can be used as a corrosion inhibitor.

[0007] Another aspect of the present invention is to provide a diazo compound that can improve polishing smoothness and increase polishing rate by reducing erosion during polishing.

[0008] Another aspect of the present invention is to provide a CMP slurry composition that can improve polishing smoothness and increase polishing rate by reducing erosion during polishing.

[0009] One aspect of the present invention relates to a diazo compound.

[0010] Example 1: The diazo compound is a compound of Formula 1 or a salt thereof:

[0011] [Formula 1]

[0012]

[0013] Among them AZ 1 and AZ 2 Independently, it is an azole-based heteroaryl group, whether substituted or unsubstituted.

[0014] R 1 and R 2 Independently hydrogen, substituted or unsubstituted C1 to C 10 Alkyl, substituted or unsubstituted C6 to C 20 aryl, substituted or unsubstituted C7 to C 20 arylalkyl groups or substituted or unsubstituted C3 to C4 20 heteroaryl; and

[0015] n and m are each an independent integer from 0 to 2.

[0016] Example 2: In Example 1, the azole heteroaryl group may be a monocyclic or polycyclic azole heteroaryl group having 1 to 6 nitrogen atoms.

[0017] Example 3: In Examples 1 and 2, the azole heteroaryl group may be diazole group, triazole group, tetraazole group, pentazole group, benzodiazole group, benzotriazole group, or naphthotriazole group.

[0018] Example 4: In Examples 1 to 3, the compound of Formula 1 may be represented by any of the following Formulas 1-1 to 1-4:

[0019] [Equation 1-1]

[0020]

[0021] [Equation 1-2]

[0022]

[0023] [Equation 1-3]

[0024]

[0025] [Equations 1-4]

[0026]

[0027] Example 5: In Examples 1 to 4, the compound or its salt can be used as a corrosion inhibitor in CMP compositions.

[0028] Another aspect of the present invention relates to a CMP slurry composition.

[0029] Example 6: The CMP slurry composition comprises: at least one solvent selected from polar and nonpolar solvents; an abrasive; and a corrosion inhibitor, wherein the corrosion inhibitor comprises a compound of Formula 1 or a salt thereof according to the present invention.

[0030] Example 7: In Example 6, the content of the corrosion inhibitor in the CMP slurry composition can be from 0.001% by weight (wt%) to 5% by weight.

[0031] Example 8: In Examples 6 and 7, the corrosion inhibitor may further include a corrosion inhibitor that does not contain a diazo group.

[0032] Example 9: In Examples 6 to 8, the corrosion inhibitor without diazo group may include at least one selected from triazole corrosion inhibitors and tetraazole corrosion inhibitors.

[0033] Example 10: In Examples 6 to 9, the composition may further comprise at least one selected from complexing agents and oxidizing agents.

[0034] Example 11: In Example 10, the composition may comprise: 0.001 wt% to 20 wt% of an abrasive; 0.001 wt% to 5 wt% of a corrosion inhibitor; 0.01 wt% to 20 wt% of a complexing agent; 0.1 wt% to 5 wt% of an oxidizing agent; and the balance being a solvent.

[0035] Example 12: In Examples 6 to 11, the CMP slurry composition may be a CMP slurry composition for polishing copper layers.

[0036] Another aspect of the present invention relates to a polishing method comprising: polishing a polishing target using a CMP slurry composition according to the present invention.

[0037] This invention provides a diazo compound that can be used as a corrosion inhibitor.

[0038] This invention provides a diazo compound that can improve polishing smoothness and increase polishing rate by reducing erosion during polishing.

[0039] The present invention provides a CMP slurry composition that can improve polishing smoothness and increase polishing rate by reducing erosion during polishing. Detailed Implementation

[0040] This invention provides a diazo compound or a salt thereof represented by Formula 1:

[0041] [Formula 1]

[0042]

[0043] Among them AZ 1 and AZ 2 Independently, it is a substituted or unsubstituted azole heteroaryl group;

[0044] R 1 and R 2 Independently hydrogen, substituted or unsubstituted C1 to C 10 Alkyl, substituted or unsubstituted C6 to C 20 aryl, substituted or unsubstituted C7 to C 20 arylalkyl groups or substituted or unsubstituted C3 to C4 20 heteroaryl; and

[0045] n and m are each an independent integer from 0 to 2.

[0046] As used in this article, “substituted or unsubstituted” means that at least one hydrogen atom in the corresponding functional group is substituted by C1 to C2. 10 Alkyl, C6 to C 20 Aryl, C7 to C 20 Arylalkyl, C3 to C 20 heteroaryl, C3 to C 10 Alicyclic groups, hydroxyl groups, amino groups, etc. are used for substitution.

[0047] The compounds of Formula 1 can be used as corrosion inhibitors. In CMP slurry compositions, corrosion inhibitors reduce the corrosion rate on the polishing target. The compounds of Formula 1 have two azole heteroaryl groups, wherein the azole heteroaryl groups are linked to a diazo group to minimize the reduction in polishing rate during polishing, while improving polishing smoothness by reducing erosion.

[0048] In one embodiment, the compound of Formula 1 is included in the CMP slurry composition as a corrosion inhibitor to minimize the reduction in polishing rate while improving polishing smoothness by reducing erosion, etc. For example, the compound of Formula 1 can be used as a corrosion inhibitor when polishing a metal layer (e.g., a copper layer).

[0049] In Formula 1, the azole heteroaryl group can be a monocyclic or polycyclic azole heteroaryl group having 1 to 6 nitrogen atoms. Here, "polycyclic" refers to an azole heteroaryl group containing at least two aryl groups, wherein at least one of the aryl groups is a heteroaryl group having a nitrogen atom as a ring-forming element, and the at least two aryl groups are fused together or connected by a single bond or C1 to C2 bond. 10 Alkyl groups are linked together. Azole heteroaryl groups may have 10 or fewer carbon atoms as the elements constituting the ring.

[0050] In one embodiment, the azole heteroaryl group may be a heteroaryl group having one nitrogen atom as a ring-forming element, a heteroaryl group having two nitrogen atoms as a ring-forming element, a heteroaryl group having three nitrogen atoms as a ring-forming element, a heteroaryl group having four nitrogen atoms as a ring-forming element, or a heteroaryl group having five nitrogen atoms as a ring-forming element. The heteroaryl group may have six or fewer carbon atoms as ring-forming elements.

[0051] For example, the azole heteroaryl group can be: diazolyl (including imidazolyl, pyrazolyl, etc.); triazolyl (including 1,2,3-triazolyl, 1,2,4-triazolyl, etc.), tetrazolyl, pentazolyl, benzodiazolyl, benzotriazolyl, or naphthotriazolyl, but is not limited thereto. Preferably, the azole heteroaryl group is benzotriazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, etc.

[0052] At least a portion of the heteroaryl groups of azoles can be hydrogenated.

[0053] In Equation 1, n and m are each independently 0, 1, or 2.

[0054] In Equation 1, R 1 and R 2 Each is independently hydrogen, substituted or unsubstituted C1 to C5 alkyl, substituted or unsubstituted C6 to C5 alkyl. 10 aryl, substituted or unsubstituted C7 to C 10 arylalkyl groups or substituted or unsubstituted C3 to C4 10 The heteroaryl group is preferably hydrogen.

[0055] In one embodiment, the compound of Formula 1 may consist of carbon, nitrogen, and hydrogen.

[0056] For example, a compound of formula 1 can be represented by any of the following formulas 1-1 to 1-4:

[0057] [Equation 1-1]

[0058]

[0059] [Equation 1-2]

[0060]

[0061] [Equation 1-3]

[0062]

[0063] [Equations 1-4]

[0064]

[0065] Salts of compounds of Formula 1 can be prepared by reacting them with acids or bases.

[0066] Compounds of Formula 1 can be prepared by typical methods known to those skilled in the art. For example, compounds of Formula 1 can be prepared by generating a diazo group or diazonium group in said azole compound having an amino group through diazotization, followed by diazo coupling or diazonium coupling with another azole compound.

[0067] The CMP slurry composition according to the present invention comprises at least one solvent selected from polar and nonpolar solvents; an abrasive; and a corrosion inhibitor, wherein the corrosion inhibitor comprises a diazo compound of formula 1 according to the present invention or a salt thereof. By using these components, the CMP slurry composition according to the present invention can improve the smoothness of the polished target by reducing erosion, etc., while increasing the polishing rate relative to the polished target. Compared with compositions not containing the corrosion inhibitor according to the present invention, the CMP slurry composition according to the present invention can maintain a high polishing rate relative to the polished target while improving its polishing smoothness. The CMP slurry composition can be applied to processes for polishing metal layers (e.g., copper layers).

[0068] The components of the CMP slurry composition (hereinafter referred to as "CMP slurry composition") according to the present invention will be described in detail below.

[0069] The corrosion inhibitor comprises a compound of Formula 1 or a salt thereof. The compound of Formula 1 or a salt thereof is substantially the same as the compound or salt thereof described above. Even using a smaller amount of the compound of Formula 1 or a salt thereof than typical triazole or tetraazole corrosion inhibitors, a significant improvement in polishing smoothness can be achieved.

[0070] The content of the compound of Formula 1 or its salt, based on the amount of all corrosion inhibitors in the CMP slurry composition, can be from 1 wt% to 100 wt%, for example, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or 100 wt%, preferably from 5 wt% to 100 wt%. Within this range, the compound of Formula 1 or its salt can ensure its inherent effect in the CMP slurry composition.

[0071] Corrosion inhibitors may also include corrosion inhibitors that do not contain a diazo group. Corrosion inhibitors that do not contain a diazo group may include at least one selected from triazole corrosion inhibitors and tetraazole corrosion inhibitors.

[0072] Triazole corrosion inhibitors may include: triazoles, such as 1,2,4-triazole, 1,2,3-triazole, etc.; diaminotriazoles, such as 3,5-diamino-1,2,4-triazole, etc.; methylbenzotriazoles, such as 5-methylbenzotriazole, 4-methylbenzotriazole, etc.; and benzotriazole compounds, such as ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, etc. Triazole corrosion inhibitors may exist in CMP slurry compositions in the form of the triazole corrosion inhibitor itself or in the form of a salt of the triazole corrosion inhibitor.

[0073] Tetraazole corrosion inhibitors may include, but are not limited to, at least one selected from tetrazolium, 5-aminotetrazole, 5-methyltetrazole, and 5-phenyltetrazole. Tetraazole corrosion inhibitors may exist in the form of the tetraazole corrosion inhibitor itself or in the form of a salt of the tetraazole corrosion inhibitor.

[0074] In the CMP slurry composition, the content of corrosion inhibitor can be from 0.001 wt% to 5 wt%, for example, 0.001 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.65 wt%, 0.7 wt%, 0.75 wt%, 0.8 wt%, 0.85 wt%, 0.9 wt%, 0.95 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%, preferably from 0.005 wt% to 0.5 wt%. Within this range, corrosion inhibitors can increase the polishing rate during polishing, while improving polishing smoothness by reducing erosion, etc.

[0075] When polishing a target using an abrasive, at least one solvent selected from polar and non-polar solvents can reduce friction on the target. The at least one solvent selected from polar and non-polar solvents may include water (e.g., ultrapure water), organic amines, organic alcohols, organic alcoholic amines, organic ethers, organic ketones, etc. Preferably, the solvent includes ultrapure water or deionized water. In the CMP slurry composition, the at least one solvent selected from polar and non-polar solvents may be present in the balance, for example, in an amount from 30% to 98% by weight.

[0076] Abrasives may include typical abrasives used for polishing. For example, an abrasive may be abrasive particles of metallic or non-metallic oxides. Abrasives may include at least one selected from, for example, colloidal silica and fumed silica, silica, alumina, cerium dioxide, titanium dioxide, and zirconium oxide. In one embodiment, the abrasive may be silica (e.g., colloidal silica), but is not limited thereto.

[0077] Abrasives may comprise spherical or non-spherical particles, wherein the average particle size (D50) of the primary particles is from 10 nanometers (nm) to 150 nm, for example, from 20 nm to 70 nm. Within this range, CMP slurry compositions can ensure a sufficient polishing rate relative to the polishing target without scratching, while improving the smoothness after polishing. As a typical particle size known to those skilled in the art, "average particle size (D50)" refers to the diameter of the particles corresponding to 50% by volume of the abrasive's volume distribution.

[0078] Abrasives may or may not undergo surface modification. Surface-modified abrasives can further improve dispersion stability or polishing rate in CMP slurry compositions. Surface modification of abrasives can be carried out by treating the abrasive with a compound for surface modification. Compounds for surface modification may include silane compounds. When the abrasive is silica, silane compounds can promote surface modification. Silane compounds may include those selected from mercapto-containing alkoxysilanes, amino-containing alkoxysilanes, tetraalkoxysilanes, and alkyl-containing compounds (having C1 to C2). 10 At least one of alkyl alkoxysilanes, but not limited thereto.

[0079] In the CMP slurry composition, the content of the abrasive can be from 0.001 wt% to 20 wt%, preferably from 0.005 wt% to 10 wt%, more preferably from 0.01 wt% to 5 wt%, and most preferably from 0.05 wt% to 3 wt%. Within this range, the CMP slurry composition can ensure a sufficient polishing rate relative to the polishing target without causing scratches, while ensuring its dispersion stability.

[0080] CMP slurry compositions may also include at least one selected from complexing agents and oxidizing agents.

[0081] Complexing agents promote the chelation of metal cations generated during polishing with metal oxides. Therefore, complexing agents can inhibit the adsorption of metal oxides onto the polishing target and suppress the generation of surface defects, while increasing the polishing rate relative to the polishing target.

[0082] Complexing agents may include at least one selected from organic acids or their salts, amino acids or their salts, alcohols (e.g., glycols, triols, and polyols), amine compounds, phosphate esters, and phosphates. Preferably, amino acids are used as complexing agents. Here, "organic acid" refers to an acid that does not contain an amino group (-NH2) compared to amino acids. As a complexing agent, amino acids ensure a higher polishing rate relative to the polishing target compared to organic acids or their salts and phosphates.

[0083] Organic acids may include organic carboxylic acids containing one or at least two carboxylic acid groups. For example, organic acids may include saturated acids (e.g., glycolic acid, lactic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, formic acid, salicylic acid, dimethylbutyric acid, octanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, etc.), maleic acid, fumaric acid, itaconic acid, phthalic acid, citric acid, etc. For example, salts of organic acids may include ammonium citrate, ammonium acetate, etc.

[0084] The amino acid may include at least one selected from glycine, alanine, serine, asparagine, glutamic acid, proline, hydroxyproline, arginine, cysteine, histidine, tyrosine, leucine, lysine, methionine, valine, isoleucine, threonine, tryptophan, and phenylalanine. Preferably, the amino acid is glycine to further improve the polishing rate relative to the copper layer.

[0085] Phosphates can include triammonium phosphate, triammonium phosphate trihydrate, etc.

[0086] In the CMP slurry composition, the content of the complexing agent can be from 0.01% by weight to 20% by weight, preferably from 0.1% by weight to 10% by weight. Within this range, the complexing agent can improve the polishing rate relative to the polishing target, the dispersion stability of the slurry composition, and the surface properties of the polishing target.

[0087] Oxidizing agents are used to oxidize the polishing target to promote polishing and form a uniform surface on the polishing target, so that the polishing target can have good surface roughness even after polishing.

[0088] The oxidizing agent may include at least one selected from inorganic percompounds, organic percompounds, bromic acid or its salts, nitric acid or its salts, chloric acid or its salts, chromic acid or its salts, iodic acid or its salts, iron or its salts, copper or its salts, rare earth metal oxides, transition metal oxides, and potassium dichromate. Here, "percompound" refers to a compound containing at least one peroxide group (-OO-) or an element in its highest oxidation state. Preferably, the oxidizing agent is a percompound. For example, the percompound may include at least one selected from hydrogen peroxide, potassium periodate, calcium persulfate, and potassium ferricyanide, preferably hydrogen peroxide.

[0089] In the CMP slurry composition, the content of the oxidant can be from 0.1% to 5% by weight, preferably from 0.5% to 3% by weight. Within this range, the CMP slurry composition can ensure polishing effect.

[0090] CMP slurry compositions may also contain a pH adjuster. The pH adjuster may include at least one organic base selected from, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, and potassium carbonate. The pH adjuster may also include at least one inorganic acid selected from, for example, nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid. In the CMP slurry composition, the content of the pH adjuster may be 1% by weight or less than 1% by weight, depending on the circumstances.

[0091] CMP slurry compositions may also contain typical additives, such as surfactants, dispersants, modifiers, surface active agents, etc.

[0092] The pH of the CMP slurry composition can be from 5 to 9, preferably from 6 to 8.

[0093] According to another aspect of the present invention, a polishing method is provided, the polishing method comprising polishing a polishing target using a CMP slurry composition according to the present invention.

[0094] The invention will now be described in more detail with reference to examples. However, it should be noted that these examples are provided for illustrative purposes only and should not be construed as limiting the invention in any way.

[0095] Example 1

[0096] 0.084 g (0.001 mol) of 3-amino-1,2,4-triazole was dissolved in 100 g of distilled water, and 0.101 g (36 wt%, 0.001 mol) of HCl was added. The resulting solution was then vigorously stirred in an ice-water bath at 0°C to 5°C. 1.3 g (5 wt%, 0.001 mol) of NaNO₂ was slowly added dropwise to the resulting solution, and the mixture was stirred for 1 hour to prepare the diazonium salt. 0.133 g (0.001 mmol) of 5-methylbenzotriazole was dissolved in a mixture of 50 g of ethanol and 50 g of ultrapure water, and 4 g of 2.5 M NaOH aqueous solution was added to the resulting solution. This solution was then added dropwise to a reactor containing the diazonium salt over 30 minutes. The resulting solution was then stirred for 1 hour, followed by vacuum drying to prepare 0.217 g of the composition represented by Formula 1-1. The preparation of the composition of Formula 1-1 was confirmed by the following nuclear magnetic resonance (NMR) results: ¹H NMR, 2.4 ppm; ³H, 7.0 ppm; ¹H, 7.6 ppm; ¹H, 7.7 ppm; ¹H, 8.0 ppm.

[0097] The CMP slurry composition was prepared by mixing 0.33 wt% of abrasive (colloidal silica, NP60, average particle size: 50 nm), 1.3 wt% of glycine (solid phase, JL Chem) as a complexing agent, 0.02 wt% of the prepared composition of Formula 1-1 as a corrosion inhibitor, 0.3 wt% of 3,5-diamino-1,2,4-triazole, and the balance ultrapure water. The pH of the CMP slurry composition was adjusted to 7.3 using a pH adjuster (nitric acid or potassium hydroxide). After pH adjustment, 1.00 wt% of hydrogen peroxide (liquid phase, Dongwoo Fine Chemistry) was added as an oxidant to the CMP slurry composition to prepare a composition for CMP slurry evaluation. In Table 1 below, "-" indicates that the corresponding component is absent.

[0098] Example 2

[0099] 0.084 g (0.001 mol) of 3-amino-1,2,4-triazole was dissolved in 100 g of distilled water, and 0.101 g (36 wt%, 0.001 mol) of HCl was added. The resulting solution was then vigorously stirred in an ice-water bath at 0°C to 5°C. 1.3 g (5 wt%, 0.001 mol) of NaNO₂ was slowly added dropwise to the resulting solution, followed by stirring for 1 hour to prepare the diazonium salt. 0.119 g (0.001 mmol) of benzotriazole was dissolved in a mixture of 50 g of ethanol and 50 g of ultrapure water, and 4 g of 2.5 M NaOH aqueous solution was added to the resulting solution, followed by dropwise addition over 30 minutes to a reactor containing the diazonium salt. The resulting solution was then stirred for 1 hour, followed by vacuum treatment and drying to prepare 0.203 g of the composition represented by Formulas 1-2.

[0100] The preparation of compositions of formulas 1-2 was confirmed based on the following NMR results. NMR results: ¹H NMR, 6.6 ppm; ²H, 7.4 ppm; ²H, 7.6 ppm.

[0101] The CMP slurry composition was prepared in the same manner as in Example 1, except that the type and content (in weight %) of each component were varied as listed in Table 1.

[0102] Example 3

[0103] 0.084 g (0.001 mol) of 3-amino-1,2,4-triazole was dissolved in 100 g of distilled water, and 0.101 g (36 wt%, 0.001 mol) of HCl was added. The resulting solution was then vigorously stirred in an ice-water bath at 0°C to 5°C. 1.3 g (5 wt%, 0.001 mol) of NaNO₂ was slowly added dropwise to the resulting solution, and the mixture was stirred for 1 hour to prepare the diazonium salt. 0.084 g (0.001 mmol) of 3-amino-1,2,4-triazole was dissolved in 100 g of ultrapure water, and 4 g of 2.5 M NaOH aqueous solution was added to the resulting solution. This solution was then added dropwise to a reactor containing the diazonium salt over 30 minutes. The resulting solution was then stirred for 1 hour, followed by vacuum treatment and drying to prepare 0.170 g of the composition represented by formulas 1-3. The preparation of the compositions of formulas 1-3 was confirmed by the following NMR results. NMR results: 1H NMR, 8.1 ppm 2H.

[0104] Except for variations in the type and amount of each component as listed in Table 1, the CMP slurry composition was prepared in the same manner as in Example 1.

[0105] Example 4

[0106] 0.084 g (0.001 mol) of 3-amino-1,2,4-triazole was dissolved in 100 g of distilled water, and 0.101 g (36 wt%, 0.001 mol) of HCl was added. The resulting solution was then vigorously stirred in an ice-water bath at 0°C to 5°C. 1.3 g (5 wt%, 0.001 mol) of NaNO₂ was slowly added dropwise to the resulting solution, and the mixture was stirred for 1 hour to prepare the diazonium salt. 0.084 g (0.001 mmol) of 4-amino-1,2,4-triazole was dissolved in 100 g of ultrapure water, and 4 g of 2.5 M NaOH aqueous solution was added to the resulting solution. This solution was then added dropwise to a reactor containing the diazonium salt over 30 minutes. The resulting solution was then stirred for 1 hour, followed by vacuum treatment and drying to prepare 0.170 g of the composition represented by formulas 1-4. The preparation of compositions of formulas 1-4 was confirmed based on the following NMR results. NMR results: ¹H NMR, 7.4 ppm ¹H, 7.7 ppm ¹H, 8.2 ppm ¹H.

[0107] Except for variations in the type and amount of each component as listed in Table 1, the CMP slurry composition was prepared in the same manner as in Example 1.

[0108] Comparative Examples 1 to 3

[0109] Except for variations in the type and amount of each component as listed in Table 1, the CMP slurry composition was prepared in the same manner as in Example 1.

[0110] Polishing evaluations were performed on the CMP slurry compositions prepared in the examples and comparative examples under the following polishing conditions. The results are shown in Table 1.

[0111] (1) Copper polishing rate (unit: angstroms / minute)

[0112] A blanket wafer with a diameter of 300 mm and including a copper layer on its silicon oxide layer was polished under the following conditions, and the polishing rate was calculated by converting the change in surface resistance before and after polishing into the etching thickness.

[0113] Polishing machine: Reflexion LK 300mm (AMAT Ltd.)

[0114] Polishing pad: IC1000

[0115] Polishing time: Polishing time varies depending on the amount of carpet polishing.

[0116] Head rotation speed: 87 revolutions per minute (rpm)

[0117] Pressure plate rotation speed: 98 rpm

[0118] Flow rate: 200 ml / min

[0119] Pressure: 1.0 psi (pounds per square inch)

[0120] Measurement of polishing amount: Surface resistance tester

[0121] (2) Etching (unit: nm): The polishing solution was placed at 60°C for 1 hour. After polishing the wafer in the same manner as in (1), the pattern profile was measured using an InSight CAP Compact Atomic Profiler (Bruker Co., Ltd.). Etching was calculated based on the height difference between the peri-oxide and cell-oxide in the 0.18 / 0.18 μm patterned region of the wafer. The scan rate was set to 100 μm / sec and the scan length was set to 2 mm.

[0122] Table 1

[0123]

[0124] As shown in Table 1, the compound of Formula 1 according to the present invention provides a CMP slurry composition that can improve polishing smoothness and polishing rate by reducing erosion during polishing.

[0125] Conversely, the compositions of the comparative examples that do not contain the compound of formula 1 have low polishing smoothness and low copper polishing rate.

[0126] It should be understood that various modifications, alterations, changes, and equivalent embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims

1. A chemical mechanical polishing slurry composition, comprising: A solvent selected from at least one of polar solvents and nonpolar solvents; Abrasives; and Corrosion inhibitors, wherein the corrosion inhibitor comprises a diazo compound of formula 1 or a salt thereof: [Formula 1] ， in: AZ 1 AZ 2 Independently for C1 to C 10 Alkyl-substituted or unsubstituted triazole, benzotriazole or naphthotriazole; R 1 and R 2 Independently hydrogen, substituted or unsubstituted C1 to C 10 Alkyl, substituted or unsubstituted C6 to C 20 aryl, substituted or unsubstituted C7 to C 20 arylalkyl groups or substituted or unsubstituted C3 to C4 20 heteroaryl; and n and m are each independent integers from 0 to 2. The phrase "substituted or unsubstituted" refers to the substitution of at least one hydrogen atom in the corresponding functional group by C1 to C2. 10 Alkyl, C6 to C 20 Aryl, C7 to C 20 Arylalkyl, C3 to C 20 heteroaryl, C3 to C 10 Alicyclic group, hydroxyl group or amino group substitution.

2. The chemical mechanical polishing slurry composition of Formula 1 according to claim 1, wherein the diazo compound of Formula 1 is represented by any one of Formulas 1-1 to 1-4: [Equation 1-1] [Equation 1-2] [Equation 1-3] [Equations 1-4] 。 3. The chemical mechanical polishing slurry composition according to claim 1, wherein the corrosion inhibitor is present in the chemical mechanical polishing slurry composition at a content of 0.001% to 5% by weight.

4. The chemical mechanical polishing slurry composition according to claim 1, wherein the corrosion inhibitor further comprises a corrosion inhibitor without a diazo group.

5. The chemical mechanical polishing slurry composition according to claim 4, wherein the diazo-free corrosion inhibitor comprises at least one selected from triazole corrosion inhibitors and tetraazole corrosion inhibitors.

6. The chemical mechanical polishing slurry composition according to claim 1 further comprises: at least one selected from complexing agents and oxidizing agents.

7. The chemical mechanical polishing slurry composition according to claim 6, comprising: 0.001 wt% to 20 wt% of the abrasive; 0.001 wt% to 5 wt% of the corrosion inhibitor; 0.01 wt% to 20 wt% of the complexing agent; 0.1 wt% to 5 wt% of the oxidizing agent; and the balance being the solvent.

8. The chemical mechanical polishing slurry composition according to claim 1, wherein the chemical mechanical polishing slurry composition is a composition for polishing copper layers.

9. A polishing method, comprising: Polishing targets are performed using the chemical mechanical polishing slurry composition as described in claim 1.

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