WO2021086015A1 - Cmp slurry composition for polishing tungsten pattern wafer, and method for polishing tungsten pattern wafer by using same - Google Patents

Abstract

Provided are a CMP slurry composition for polishing a tungsten pattern wafer, and a method for polishing a tungsten pattern wafer by using same, the CMP slurry composition comprising: a polar solvent and/or a nonpolar solvent; an abrasive; a compound of chemical formula 1; and a polycarboxylic acid, wherein the composition comprises the compound of chemical formula 1 in an amount of approximately 0.001-2 wt% and the polycarboxylic acid in an amount of approximately 0.001-5 wt%.

Description

CMP slurry composition for polishing tungsten pattern wafer and method for polishing tungsten pattern wafer using the same

The present invention relates to a CMP slurry composition for polishing a tungsten pattern wafer and a method for polishing a tungsten pattern wafer using the same. More specifically, the present invention provides a CMP slurry composition for polishing a tungsten pattern wafer and a tungsten pattern using the same, which minimizes a decrease in tungsten polishing rate and improves the stability of a slurry while improving a tungsten recess when polishing a tungsten pattern. It relates to a wafer polishing method.

Chemical mechanical polishing (CMP) compositions and methods for polishing (or planarizing) the surface of a substrate are well known in the art. The polishing composition for polishing a metal layer (eg, tungsten) on a semiconductor substrate may include abrasive particles suspended in an aqueous solution and a chemical accelerator such as an oxidizing agent, a chelating agent, a catalyst, and the like.

On the other hand, it is important to increase the polishing rate of tungsten in the tungsten polishing of the metal layer. However, as much as improving the polishing rate, it is also important to reduce the recess of the polished tungsten. Conventionally, in order to reduce the recess, an amino acid compound has been added as a corrosion inhibitor to a polishing composition. However, when the amino acid is added, the recess can be reduced, but there are many cases of causing a side effect of reducing the polishing rate of tungsten.

An object of the present invention is to provide a CMP slurry composition for polishing a tungsten pattern wafer that minimizes a decrease in a tungsten polishing rate while improving a tungsten recess during tungsten pattern polishing.

Another object of the present invention is to provide a CMP slurry composition for polishing a tungsten pattern wafer with improved slurry stability.

Another object of the present invention is to provide a CMP slurry composition for polishing a tungsten pattern wafer with improved slurry stability.

The CMP slurry composition for polishing a tungsten pattern wafer of the present invention comprises at least one of a polar solvent and a non-polar solvent; abrasive; A compound represented by the following formula 1; And a polycarboxylic acid, wherein the compound of Formula 1 is included in about 0.001% to 2% by weight of the composition, and the polycarboxylic acid is included in about 0.001% to 5% by weight of the composition:

[Formula 1]

(In Chemical Formula 1,

R ^1, R ² are, each independently, a hydrogen, a hydroxyl group (-OH), the charged oxygen negatively (-O ^-), a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group And is selected from the group consisting of an aryloxy group,

R ^1, R ² is at least one of the oxygen (-O ^-) charged by hydroxyl or negative and,

X is -O-, -S-, -NH-, -C(=O)-, -(C=O)O-, -(C=O)NH-, -NH(C=NH ₂ ⁺ )- NH-, an alicyclic group containing at least one nitrogen or an aromatic group containing at least one nitrogen,

n is 0 or 1,

L is a single bond or a divalent linking group,

C ^* is a stereocentric carbon,

R ³ is -C(=O)OH, -C(=O)O ^- , or -C(=O)ORa (wherein Ra is a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, or a monovalent aromatic hydrocarbon group )ego,

R ⁴ is -NH ₂ , -NH ₃ ⁺ or -NHRb (wherein Rb is a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, or a monovalent aromatic hydrocarbon group).

The method of polishing a tungsten pattern wafer of the present invention includes polishing a tungsten pattern wafer using the CMP slurry composition for polishing a tungsten pattern wafer of the present invention.

The present invention provides a CMP slurry composition for polishing a tungsten pattern wafer that minimizes a decrease in a tungsten polishing rate while improving a tungsten recess when polishing a tungsten pattern.

The present invention provides a CMP slurry composition for polishing a tungsten pattern wafer with improved slurry stability.

In the present specification, "substituted" in "substituted or unsubstituted" means that at least one hydrogen atom among the functional groups is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group, an alkenyl group having 2 to 10 carbon atoms, or Haloalkenyl group, C2-C10 alkynyl or haloalkynyl group, C3-C10 cycloalkyl group, C3-C10 cycloalkenyl group, C6-C10 Substituted by any one of an aryl group, a C7 to C10 arylalkyl group, a C1 to C10 alkoxy group, a C6 to C10 aryloxy group, an amino group, halo, cyano group, or thiol group Means that it has become.

When describing the numerical range in the present specification, "X to Y" means X or more and Y or less.

The inventors of the present invention improve tungsten recesses during tungsten pattern polishing, minimize tungsten polishing rate reduction, and reduce the slurry It was confirmed that the stability was improved and the present invention was completed.

The CMP slurry composition for polishing a tungsten pattern wafer of the present invention (hereinafter, referred to as "CMP slurry composition") includes at least one of a polar solvent and a non-polar solvent; abrasive; A compound represented by the following formula (1); And a polycarboxylic acid, wherein the compound of Formula 1 is included in an amount of about 0.001% to 2% by weight of the composition, and the polycarboxylic acid is included in an amount of about 0.001% to 5% by weight of the composition.

Hereinafter, the constituent components of the CMP slurry composition according to the present invention will be described in detail.

At least one of a polar solvent and a non-polar solvent can reduce friction when polishing a tungsten pattern wafer with an abrasive. At least one of a polar solvent and a non-polar solvent may be water (for example, ultrapure water or deionized water), organic amines, organic alcohols, organic alcoholamines, organic ethers, organic ketones, and the like. Preferably, ultrapure water or deionized water may be used. At least one of a polar solvent and a non-polar solvent may be included in the residual amount of the CMP slurry composition.

The abrasive can polish the insulating layer film (eg, silicon oxide film) and the tungsten metal film at a high polishing rate. Specifically, the abrasive is a metal or non-metal oxide abrasive, and may include at least one of silica, alumina, ceria, titania, and zirconia. In particular, silica can be used as an abrasive.

The abrasive is spherical or non-spherical particles, and the average particle diameter (D50) of the primary particles may be about 10 nm to 200 nm, for example, about 40 nm to 120 nm. Within the above range, the polishing rate for the insulating layer film and the tungsten metal film as the polishing targets of the present invention may be increased, and surface defects (scratches, etc.) may not occur after polishing. The "average particle diameter (D50)" refers to a typical particle diameter known to those skilled in the art, and refers to a particle diameter of 50% by weight when the abrasive is distributed on a weight basis.

The abrasive is from about 0.001% to 20% by weight, preferably from about 0.01% to 10% by weight, more preferably from about 0.01% to 5% by weight, most preferably from about 0.05% to 5% by weight in the CMP slurry composition. It can be included in %. Within the above range, the insulating layer film and the tungsten metal film may be polished at a sufficient polishing rate, scratches may not be generated, and dispersion stability of the composition may be good.

The compound of Formula 1 below is about 0.001% to 2% by weight of the composition (for example, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, or 2% by weight). In the above range, recesses are reduced during tungsten polishing, and a reduction in tungsten polishing rate is minimized. Preferably, the compound of Formula 1 below may be included in an amount of about 0.005% to 0.2% by weight, more preferably about 0.005% to 0.05% by weight of the composition.

[Formula 1]

(In Chemical Formula 1,

R ^1, R ² are each independently hydrogen, a hydroxyl group (-OH), the charged oxygen negatively (-O ^-), a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group, and It is selected from the group consisting of an aryloxy group,

R ^1, R ² is at least one of the oxygen (-O ^-) charged by hydroxyl or negative and,

X is -O-, -S-, -NH-, -C(=O)-, -(C=O)O-, -(C=O)NH-, -NH(C=NH ₂ ⁺ )- NH-, an alicyclic group containing at least one nitrogen, or an aromatic group containing at least one nitrogen,

n is 0 or 1,

L is a single bond or a divalent linking group,

C ^* is a stereocentric carbon,

R ³ is -C(=O)OH, -C(=O)O ^- , or -C(=O)ORa (wherein Ra is a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, or a monovalent aromatic hydrocarbon group )ego,

R ⁴ is -NH ₂ , -NH ₃ ⁺ or -NHRb (wherein Rb is a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, or a monovalent aromatic hydrocarbon group).

In one embodiment, in Formula 1, R ³ may be -C(=O)O ^- , and R ⁴ may be -NH ₃ ^+. In this case, the stereocentric carbon C ^* portion of the compound of Formula 1 is derived from an amino acid, so that it is easy to manufacture, and there may be an effect of reducing the tungsten etching (corrosion) rate. In addition, in the compound of Formula 1, the phosphorus-containing functional group in the composition represents an anionic functional group, and the stereocentric carbon C ^* exhibits zwitterionicity, thereby reducing the tungsten etching (corrosion) rate and simultaneously realizing a chelate against a metal catalyst. There is. The "amino acid" may be serine, tyrosine, cysteine, or the like, but is not limited thereto.

In another embodiment, in Formula 1, R ³ may be -C(=O)OH, and R ⁴ may be -NH _2. In this case, the compound of Formula 1 is derived from an amino acid, so that it is easy to manufacture, and there may be an effect of reducing tungsten etching (corrosion) rate.

In one embodiment, in Formula 1, R ^1, R ² are each independently a hydroxyl group (-OH), the charged oxygen negatively (-O ^-) is selected from an alkoxy group and aryloxy group the group consisting of, R ^1, at least one of R ² is the oxygen (-O ^-) charged by a hydroxyl group or a sound can be a. Formula 1 may provide a chelating effect on a metal catalyst by having a phosphate group, a phosphinate group, or a phosphonate group in the composition.

In one embodiment, the compound of Formula 1 may be, but is not limited to, isomers alone, or a mixture of two isomers (racemic) at the ^{stereocentric carbon C *.}

In Formula 1, the "monovalent aliphatic hydrocarbon group" is a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. It may be an alkyl group of.

In Formula 1, the "monovalent alicyclic hydrocarbon group" is a substituted or unsubstituted alicyclic hydrocarbon group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. It can be an alicyclic hydrocarbon group.

In Formula 1, the "monovalent aromatic hydrocarbon group" is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, preferably 6 carbon atoms To a C10 aryl group or a C7 to C10 arylalkyl group.

In Formula 1, the "alkoxy group" is a functional group in which a divalent oxygen is connected to the monovalent aliphatic hydrocarbon group or the monovalent alicyclic hydrocarbon group, for example, a substituted or unsubstituted linear or branched C1 to C20 It may be an alkoxy group of, preferably an alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

In Formula 1, the "aryloxy group" is a functional group in which a divalent oxygen is connected to the monovalent aromatic hydrocarbon group, for example, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, for example 6 carbon atoms To a C10 aryloxy group.

In Formula 1, the "alicyclic group containing at least one nitrogen" refers to an alicyclic group containing at least one nitrogen and having 2 to 6 carbon atoms and preferably 2 to 5 carbon atoms forming a ring.

In Formula 1, the "aromatic group containing at least one nitrogen" refers to an aromatic group containing at least one nitrogen and having 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms, forming an aromatic ring. The aromatic group containing one or more nitrogen may be in a monocyclic form or may be in a form in which two or more aromatic groups are fused.

In Formula 1, the "divalent linking group" defined for L means that the above-described "monovalent aliphatic hydrocarbon group", "monovalent alicyclic hydrocarbon group", and "monovalent aromatic hydrocarbon group" are each modified in a divalent form. it means. For example, "divalent linking group" is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Alkylene group; A substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, preferably a cycloalkylene group having 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms; A substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted arylalkylene group having 7 to 20 carbon atoms, preferably an arylene group having 6 to 10 carbon atoms, 7 carbon atoms To a C10 arylalkylene group.

In one embodiment, the compound of Formula 1 may be derived from the following Formula 1-1 or the following Formula 1-2, but is not limited thereto.

[Formula 1-1]

[Formula 1-2]

(In Chemical Formulas 1-1 and 1-2, C* is a stereogenic central carbon).

The polycarboxylic acid is about 0.001% to 5% by weight of the composition (e.g., 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, or 5% by weight). In the above range, the stability of the slurry is improved, and there may be a chelating effect on the metal catalyst. Preferably, the polycarboxylic acid may be contained in an amount of 0.005% to 0.2% by weight, more preferably 0.005% to 0.1% by weight of the composition.

The polycarboxylic acid may include at least one of saturated or unsaturated aliphatic polycarboxylic acid, alicyclic polycarboxylic acid, aromatic polycarboxylic acid, and hetero polycarboxylic acid. Saturated or unsaturated aliphatic polycarboxylic acid is a saturated or unsaturated aliphatic polycarboxylic acid having 2 to 20 carbon atoms, for example, malonic acid, maleic acid, malic acid, oxalic acid, fumaric acid, succinic acid, glutaric acid. , Citric acid, isocitric acid, oxalic acid, adipic acid, tartaric acid, itaconic acid, citraconic acid, may include one or more of mesaconic acid. The alicyclic polycarboxylic acid is an alicyclic polycarboxylic acid having 3 to 10 carbon atoms, for example, cyclopentanetetracarboxylic acid, cyclopentane tricarboxylic acid, cyclopentanedicarboxylic acid, and cyclobutane tetracarboxylic acid. It may contain at least one of an acid, a cyclobutane tricarboxylic acid, and a cyclobutane dicarboxylic acid. Aromatic polycarboxylic acid is a monocyclic or polycyclic (including a fused or linked form) aromatic polycarboxylic acid having 6 to 20 carbon atoms, for example terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid It may contain one or more of. Heteropolycarboxylic acid is a C2-C20 heteropolycarboxylic acid containing one or more nitrogen or oxygen, for example, PDTA (1,3-propylenediaminetetraacetic acid), EDTA (ethylenediaminetetraacetic acid), DTPA ( diethylenetriaminepentaacetic acid), NTA (nitrilotriacetic acid), EDDS (ethylenediamine-N,N'-disuccinic acid), aspartic acid, glutamic acid, tetrahydrofuran tetracarboxylic acid, and tetrahydrofuran dicarboxylic acid. Preferably, the polycarboxylic acid is a saturated or unsaturated aliphatic polycarboxylic acid having 2 to 5 carbon atoms, and may include at least one of malonic acid, maleic acid, and malic acid.

The CMP slurry composition may further include amino acids.

Amino acids can improve long-term storage stability by stably maintaining the pH of the CMP slurry composition so that the insulating layer film is polished. In addition, amino acids may provide convenience in supply, maintenance, and storage of the CMP slurry composition by maintaining the polishing rate ratio between the insulating layer film and the tungsten film.

The amino acid may include, but is not limited to, one or more of glycine, isoleucine, leucine, phenylalanine, methionine, threonine, tryptophan, valine, alanine, arginine, cysteine, glutamine, histidine, proline, serine, tyrosine, and lysine.

Amino acids are about 0.001% to 10%, preferably about 0.01% to 5%, more preferably about 0.01% to 2%, most preferably about 0.01% to 0.5% by weight of the CMP slurry composition. It may be included in weight percent. In the above range, erosion and recess can be simultaneously improved when polishing a tungsten pattern wafer.

The CMP slurry composition may further include at least one of an iron ion compound, an iron ion complex, and a hydrate thereof.

An iron ion compound, an iron ion complex compound, or a hydrate thereof can improve the polishing rate of the tungsten metal film and the insulating layer film. The iron ion compound or its complexes act as an oxidizing agent for the tungsten metal film to improve the polishing rate of the tungsten metal film, and the etching rate for the tungsten metal film is low to prevent gaps from occurring and to increase the polishing speed for the insulating layer film. have.

The iron ion compound may include an iron trivalent cation containing compound. The iron trivalent cation-containing compound is not particularly limited as long as it is a compound in which the iron trivalent cation exists as a free cation in an aqueous solution state. For example, the iron trivalent cation-containing compound may include one or more of iron chloride (FeCl ₃ ), iron nitrate (Fe(NO ₃ ) ₃ ), and iron sulfate (Fe ₂ (SO ₄ ) ₃ ), but this Not limited.

The iron ion complex may include an iron trivalent cation-containing complex. The iron trivalent cation-containing complex compound may include a compound formed by reacting an iron trivalent cation with an organic compound or inorganic compound having at least one functional group among carboxylic acids, phosphoric acids, sulfuric acids, amino acids, and amines in an aqueous solution. have. The organic or inorganic compounds are citrate, ammonium citrate, paratoluenesulfonic acid (pTSA), PDTA (1,3-propylenediaminetetraacetic acid), EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), NTA (nitrilotriacetic acid), EDDS (ethylenediamine-N,N'-disuccinic acid) may be used, but is not limited thereto. Specific examples of iron trivalent cation-containing complexes include ferric citrate, ferric ammonium citrate, Fe(III)-pTSA, Fe(III)-PDTA, and Fe(III)-EDTA. However, it is not limited thereto.

At least one of an iron ion compound, an iron ion complex, and a hydrate thereof is about 0.001% to 10% by weight (e.g., 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009) in the CMP slurry composition. , 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7 , 8, 9, or 10% by weight), preferably about 0.001% to 5% by weight, more preferably about 0.001% to 1% by weight, most preferably about 0.001% to 0.5% by weight. I can. Within the above range, the tungsten metal film may exhibit an appropriate oxidizing power, thereby increasing the polishing rate of the tungsten metal film.

The CMP slurry composition may further include an oxidizing agent.

The oxidizing agent may oxidize the insulating layer film and the tungsten metal film to facilitate polishing of the insulating layer film and the tungsten metal film, and may make the surface of the insulating layer film and the tungsten metal film evenly so that the surface roughness is good even after polishing.

The oxidizing agent is an inorganic percompound, an organic percompound, bromic acid or a salt thereof, nitric acid or a salt thereof, chloric acid or a salt thereof, chromic acid or a salt thereof, iodic acid or a salt thereof, iron or a salt thereof, copper or a salt thereof, a rare earth metal oxide , Transition metal oxide, and potassium dichromate. The "per-compound" is a compound containing one or more peroxidation groups (-O-O-) or an element in the highest oxidation state. Preferably, it is possible to use a supercompound as an oxidizing agent. For example, the percompound may be at least one of hydrogen peroxide, potassium periodide, calcium persulfate, and potassium ferricyanide, preferably hydrogen peroxide.

The oxidizing agent may be included in about 0.01% to 20% by weight, preferably about 0.05% to 10% by weight, more preferably about 0.1% to 5% by weight of the CMP slurry composition. Within the above range, it is possible to improve the polishing selectivity.

The CMP slurry composition may have a pH of about 1 to 5 (eg, 1, 2, 3, 4, or 5), preferably about 2 to 4. In the above range, tungsten metal oxidation may easily occur, so that the polishing rate may not be easily reduced.

The CMP slurry composition may further include a pH adjuster to adjust the pH. The pH adjusting agent may include one or more of inorganic acids, such as nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid, and organic acids, such as organic acids having a pKa value of about 6 or less, may include, for example, one or more of acetic acid and phthalic acid. . The pH adjusting agent may include one or more of a base such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, and potassium carbonate.

The CMP slurry composition may further contain conventional additives such as surfactants, dispersants, modifiers, and surface active agents.

The method of polishing a tungsten pattern wafer of the present invention includes polishing a tungsten pattern wafer using the CMP slurry composition for polishing a tungsten pattern wafer of the present invention.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this has been presented as a preferred example of the present invention and cannot be construed as limiting the present invention in any sense.

The CMP slurry composition for polishing a tungsten pattern wafer prepared in Examples was subjected to polishing evaluation under the following polishing evaluation conditions. The results are shown in Tables 4 to 5 below.

[Polishing evaluation conditions]

1.Grinding machine: Reflexion 300mm (AMAT)

2. Polishing conditions

-Polishing pad: IC1010/SubaIV Stacked (Rodel)

-Head speed: 101rpm

-Platen speed: 100rpm

-Pressure: 2.0psi

-Retainer Ring Pressure: 8psi

-Slurry flow rate: 200ml/min

-Polishing time: 60 seconds

3. Polishing target

-Use of commercially available tungsten pattern wafer (MIT 854, 300mm)

-Blanket wafers are manufactured by sequentially depositing titanium nitride (TiN) and tungsten at 300Å and 6,000Å, respectively, on a polycrystalline silicon substrate.

4. Analysis method

-Recess (unit: nm): Calculate the recess by measuring the 0.18 x 0.18μm area profile of the pattern with an Atomic Force Microscope (Uvx-Gen3, Bruker)

-Polishing speed (unit: Å min): Polishing speed is calculated by converting the difference in film thickness before and after polishing from the electric resistance value when evaluated under the above polishing conditions.

Example 1

This example shows the effect of polycarboxylic acid on the stability of the slurry containing Formula 1. The composition is shown in Table 1 below. The abrasive is a silica particle having an average particle diameter (D50) of about 95 nm and a charge of about 35 mV. Deionized water was used as a solvent. From the particle size data provided in Table 2 below, the slurry of the present invention containing a polycarboxylic acid can be confirmed to have excellent stability compared to a slurry containing no polycarboxylic acid. The particle size of the high temperature storage slurry was stored in an oven at 40° C. for 7 days and then measured using a particle size analyzer (Malvern, zetasizer Nano).

Slurry	type	pH	Abrasive (% by weight)	Catalyst (% by weight)	Phosphorus-containing amino acids (% by weight)	Polycarboxylic acid (% by weight)
1-A	The present invention	2.5	Silica (0.2)	FNA(0.01)	0.02	0.01
1-B	The present invention	2.5	Silica (0.2)	FNA(0.01)	0.02	0.03
1-C	The present invention	2.5	Silica (0.2)	FNA(0.01)	0.02	0.05
1-D	For comparison	2.5	Silica (0.2)	FNA(0.01)	0.02	-
FNA = iron nitrate hydrate, phosphorus-containing amino acid = formula 1-1, polycarboxylic acid = malonic acid

Slurry	type	Initial particle size (nm)	High temperature storage particle size (nm)
1-A	The present invention	95	99
1-B	The present invention	94	95
1-C	The present invention	96	95
1-D	For comparison	95	197

Example 2

This example shows the effect of Formula 1 on tungsten etching (corrosion) rate and polishing rate. The composition is shown in Table 3 below. From the tungsten etching (corrosion) rate provided in Table 4 below, it can be seen that the slurry of the present invention containing Chemical Formula 1 has a low tungsten etching (corrosion) rate compared to other materials that do not contain Chemical Formula 1 or have a phosphorus functional group. In addition, from the tungsten polishing rate provided in Table 4, Formula 1, which is a phosphorus-containing amino acid of the present invention, exhibits excellent tungsten etching (corrosion) rate and relatively high tungsten polishing rate compared to other amino acids. In addition, as provided in Table 4, when the phosphorus-containing amino acid of the present invention, Formula 1, was used in the same number of moles, the polishing rate of tungsten was higher than that of the phosphorus-containing compound and amino acid. The tungsten etching rate was performed under the condition of 50°C, and the difference in film thickness before and after etching was converted from the electric resistance value.

Slurry	type	pH	Phosphorus-containing amino acids (mM) (% by weight)	Phosphorus-containing compound (mM) (% by weight)	Amino acid (mM) (% by weight)
2-A	The present invention	2.5	Formula 1-1 (0.5) (0.0092)	-	-
2-B	The present invention	2.5	Formula 1-1 (1.0) (0.0185)	-	-
2-C	The present invention	2.5	Formula 1-2 (1.0) (0.0199)	-	-
2-D	For comparison	2.5	-	OPEA (1.0)(0.0141)	-
2-E	For comparison	2.5	-	AEP (1.0)(0.0125)	-
2-F	For comparison	2.5	-	-	Lysine (1.0) (0.0146)
2-G	For comparison	2.5		-	Arginine (1.0) (0.0174)
2-H	For comparison	2.5	-	-	-
Basic composition: Silica (0.2% by weight), iron nitrate citrate (0.01% by weight), malonic acid (0.02% by weight), residual amount of deionized water* OPEA = O-Phosphoethanolamine, AEP = Aminoethylphosphonic acid* Tungsten etching rate and polishing rate Proceeds in the presence of hydrogen peroxide (2.0%)

Slurry	type	Tungsten etching rate (Å/min)	Tungsten polishing rate (Å/min)
2-A	The present invention	20	4652
2-B	The present invention	16	4569
2-C	The present invention	18	4224
2-D	For comparison	58	4433
2-E	For comparison	51	3655
2-F	For comparison	24	2832
2-G	For comparison	15	2741
2-H	For comparison	134	4847

Example 3

This example shows the effect of Formula 1 on tungsten recesses. From the tungsten recesses provided in Table 5, it can be seen that the slurry of the present invention containing Chemical Formula 1 has superior tungsten recesses compared to other materials that do not contain Chemical Formula 1 or have a phosphorus functional group.

Slurry	type	pH	Phosphorus-containing amino acids (%)	Phosphorus-containing compound (%)	Recess (nm)
3-A	The present invention	2.5	Formula 1-1 (0.01)	-	21.3
3-B	The present invention	2.5	Formula 1-1 (0.02)	-	19.1
3-C	The present invention	2.5	Formula 1-2 (0.02)	-	21.0
3-D	For comparison	2.5	-	OPEA (0.02)	24.8
3-E	For comparison	2.5	-	AEP (0.02)	25.4
3-F	For comparison	2.5	-	-	30.1
Basic composition: silica (0.2% by weight), iron nitrate citrate (0.01% by weight), malonic acid (0.02% by weight), biocide (0.06% by weight), residual amount of deionized water * OPEA = O-Phosphoethanolamine, AEP = Aminoethylphosphonic acid* tungsten polishing proceeds in the presence of hydrogen peroxide (2.0%)

Simple modifications or changes of the present invention can be easily implemented by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (10)

1. At least one of a polar solvent and a non-polar solvent; abrasive; A compound represented by the following formula 1; And as a CMP slurry composition for polishing a tungsten pattern wafer comprising a polycarboxylic acid,

   The compound of Formula 1 is included in about 0.001% to 2% by weight of the composition, and the polycarboxylic acid is included in about 0.001% to 5% by weight of the composition, CMP slurry for polishing a tungsten pattern wafer Composition:

   [Formula 1]

   

   (In Chemical Formula 1,

   R ^1, R ² are, each independently, a hydrogen, a hydroxyl group (-OH), the charged oxygen negatively (-O ^-), a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group And is selected from the group consisting of an aryloxy group,

   R ^1, R ² is at least one of the oxygen (-O ^-) charged by hydroxyl or negative and,

   X is -O-, -S-, -NH-, -C(=O)-, -(C=O)O-, -(C=O)NH-, -NH(C=NH ₂ ⁺ )- NH-, an alicyclic group containing at least one nitrogen or an aromatic group containing at least one nitrogen,

   n is 0 or 1,

   L is a single bond or a divalent linking group,

   C* is a stereocentric carbon,

   R ³ is -C(=O)OH, -C(=O)O ^- , or -C(=O)ORa (wherein Ra is a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, or a monovalent aromatic hydrocarbon group )ego,

   R ⁴ is -NH ₂ , -NH ₃ ⁺ or -NHRb (wherein Rb is a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, or a monovalent aromatic hydrocarbon group).
2. The method of claim 1, wherein in Formula 1, R ³ is -C(=O)OH, and R ⁴ is -NH _{2. The} CMP slurry composition for polishing a tungsten pattern wafer.
3. The method of claim 1, wherein in Formula 1, R ^1, R ² are each independently a hydroxyl group (-OH), the charged oxygen negatively (-O ^-) is selected from an alkoxy group and aryloxy group the group consisting of, R ^1, at least one of R ² is a hydroxyl group or a negative charged oxygen (-O ^-) is like a tungsten patterned wafer polishing CMP slurry composition.
4. The method of claim 1, wherein the compound of Formula 1 is derived from any one of the following Formulas 1-1 and 1-2, the CMP slurry composition for polishing a tungsten pattern wafer:

   [Formula 1-1]

   

   [Formula 1-2]

   
5. The CMP slurry composition for polishing a tungsten pattern wafer according to claim 1, wherein the polycarboxylic acid comprises a saturated or unsaturated aliphatic polycarboxylic acid having 2 to 20 carbon atoms.
6. The method of claim 5, wherein the polycarboxylic acid is malonic acid, maleic acid, malic acid, oxalic acid, fumaric acid, succinic acid, glutaric acid, citric acid, isocitric acid, oxalic acid, adipic acid, tartaric acid, itaconic acid, citracone CMP slurry composition for polishing a tungsten pattern wafer containing at least one of acid and mesaconic acid.
7. The CMP slurry composition for polishing a tungsten pattern wafer according to claim 1, wherein the CMP slurry composition has a pH of about 1 to 5.
8. The CMP slurry composition for polishing a tungsten pattern wafer according to claim 1, wherein the CMP slurry composition further comprises at least one of an iron ion compound, an iron ion complex, and a hydrate thereof.
9. The CMP slurry composition for polishing a tungsten pattern wafer according to claim 8, wherein at least one of the iron ion compound, an iron ion complex, and a hydrate thereof is contained in an amount of about 0.001% to 10% by weight in the CMP slurry composition. .
10. A tungsten pattern wafer polishing method comprising the step of polishing a tungsten pattern wafer using the CMP slurry composition for polishing a tungsten pattern wafer according to any one of claims 1 to 9.