KR20200020397A - Cmp slurry composition for polishing metal and method for polishing metal using the same - Google Patents

Abstract

Provided are a CMP slurry composition for polishing metal wiring and a metal wiring polishing method using the same. The CMP slurry composition for polishing metal wiring includes: at least one of a polar solvent and a non-polar solvent; metal oxide abrasives; and at least one kind of compound among chemical formula 1, chemical formula 2, and chemical formula 3. The present invention can increase the storage stability of the CMP slurry composition.

Description

CMP slurry composition for metal wire polishing and metal wire polishing method using the same {CMP SLURRY COMPOSITION FOR POLISHING METAL AND METHOD FOR POLISHING METAL USING THE SAME}

The present invention relates to a metal wire polishing CMP slurry composition and a metal wire polishing method using the same. More specifically, the present invention improves the storage stability of the CMP slurry composition, prevents filter clogging during filtration of the CMP slurry composition in the semiconductor manufacturing process, prevents contamination of semiconductor manufacturing equipment, and prevents agglomeration of metal oxide abrasives, thereby improving polishing performance. The present invention relates to a CMP slurry composition for metal wiring polishing, and a metal wiring polishing method using the same, by which the processability of a semiconductor manufacturing process can be improved by not lowering.

In the CMP process, the surface of the wafer is planarized using a polishing pad and a slurry composition during semiconductor manufacturing. The polishing agent is brought into contact with the polishing pad and the wafer, and then the polishing pad and the wafer are subjected to orbital motion by mixing rotational and linear motion. It is a process of polishing using a slurry composition containing. The semiconductor manufacturing process is a precision process, and it is important to improve and maintain polishing performance by the CMP slurry composition. Therefore, before polishing, the CMP slurry composition must be filtered by a filter having a predetermined pore size to remove impurities and the like. By the way, the CMP slurry composition may be used immediately after the manufacture, but in most cases, the CMP slurry composition may not be used immediately after the manufacture. At this time, if there is microbial propagation in the CMP slurry composition during the storage period, there is a filter clogging during filtration of the CMP slurry composition, the semiconductor manufacturing equipment itself may be contaminated and the processability may be degraded. Performance may be impaired.

The object of the present invention is It is to provide a CMP slurry composition for metal wire polishing that can enhance the storage stability of the CMP slurry composition.

Another object of the present invention is to improve the processability of the semiconductor manufacturing process by eliminating filter clogging during the filtration of the CMP slurry composition in the semiconductor manufacturing process, preventing contamination of the semiconductor manufacturing equipment, and preventing agglomeration of the metal oxide abrasive to reduce polishing performance. It is to provide a CMP slurry composition for metal wire polishing.

The metal wire polishing CMP slurry composition of the present invention is at least one of a polar solvent and a nonpolar solvent; Metal oxide abrasives; And one or more compounds of Formula 1, Formula 2, and Formula 3:

<Formula 1>

<Formula 2>

<Formula 3>

The metal wire polishing method of the present invention may include polishing the metal wire polishing CMP slurry composition of the present invention.

The present invention The CMP slurry composition for metal wiring polishing which can improve the storage stability of a CMP slurry composition was provided.

The present invention is a metal that can improve the processability of the semiconductor manufacturing process by avoiding filter clogging during the filtration of the CMP slurry composition in the semiconductor manufacturing process, preventing contamination of the semiconductor manufacturing equipment, and preventing agglomeration of the metal oxide abrasive to reduce polishing performance. A wire polishing CMP slurry composition was provided.

MEANS TO SOLVE THE PROBLEM This inventor is one or more of a polar solvent and a nonpolar solvent; Including the metal oxide abrasive, and in the pH range of the metal wire polishing CMP composition of the present invention, by containing at least one compound of the following formula (1), (2), (3) by preventing the microbial contamination and / or breeding To improve the storage stability of the CMP slurry composition, to prevent filter clogging during the filtration of the CMP slurry composition in the semiconductor manufacturing process, to prevent contamination of semiconductor manufacturing equipment, and to prevent agglomeration of metal oxide abrasives, thereby preventing polishing performance. It was confirmed that the processability of the process can be improved, and completed the present invention. The metal wire polishing CMP slurry composition of the present invention may be used for metal wire polishing applications such as copper, tungsten, titanium, and aluminum, but is not limited thereto.

Hereinafter, the component of the CMP slurry composition for metal wiring polishing of this invention is demonstrated in detail.

The metal wire polishing CMP slurry composition of the present invention is at least one of a polar solvent and a nonpolar solvent; Metal oxide abrasives; And one or more compounds of Formula 1, Formula 2, and Formula 3.

At least one of the polar solvent and the nonpolar solvent may reduce friction when polishing with a metal oxide abrasive. At least one of the polar solvent and the nonpolar solvent may be water (eg ultrapure or deionized water), organic amines, organic alcohols, organic alcoholamines, organic ethers, organic ketones and the like. Preferably ultrapure water or deionized water can be used.

At least one of the polar solvent and the nonpolar solvent may be included in the balance in the CMP slurry composition.

Metal oxide abrasives can polish metal wires at high polishing rates. The metal oxide abrasive may comprise one or more of silica, alumina, ceria, titania, zirconia. Preferably, colloidal silica may be used among silica as the metal oxide abrasive.

The metal oxide abrasive may be spherical or non-spherical particles having an average particle diameter (D50) of 10 nm to 150 nm, for example, 20 nm to 50 nm. In the above range, it is possible to achieve a sufficient polishing rate for the metal wiring and to prevent scratches from occurring. The "average particle diameter (D50)" means a common particle diameter known to those skilled in the art, and means a particle size of 50% by weight of the abrasive when the abrasive is distributed by weight.

The metal oxide abrasive may comprise 0.01 to 20 weight percent, preferably 0.02 to 15 weight percent, more preferably 0.05 to 10 weight percent in the CMP slurry composition. It is possible to achieve a sufficient polishing rate for the metal wiring in the above range, it can be easy to adjust the polishing rate.

One or more compounds of Formula 1, Formula 2, and Formula 3 may be included in a CMP slurry composition having a pH range of the present invention to prevent contamination of microorganisms without degrading the polishing performance and storage stability of the CMP composition. have.

<Formula 1>

<Formula 2>

<Formula 3>

The compounds of Formula 1, Formula 2, and Formula 3 may block the growth of microorganisms such as bacteria, yeast or fungi. Specifically, these compounds can block the growth of Aspergillus niger species among microorganisms.

The compound of Formula 1 is a peroxide compound having a phthalimido group and a peroxy group (-OO-), and when included in the CMP slurry composition, may block the growth of microorganisms without degrading the polishing performance and storage stability of the CMP slurry composition. .

The compound of Formula 2 is an aldehyde of an unsaturated lower hydrocarbon, when included in the CMP slurry composition can block the growth of microorganisms without reducing the polishing performance and storage stability of the CMP slurry composition.

The compound of Formula 3 is a triazole compound having a dioxolane, when included in the CMP slurry composition can block the growth of microorganisms without reducing the polishing performance and storage stability of the CMP slurry composition.

The compounds of Formula 1, Formula 2, and Formula 3 may also be prepared by commercial methods or commercially available products known to those skilled in the art.

At least one compound of Formula 1, Formula 2, and Formula 3 is 0.001% to 1% by weight, preferably 0.01% to 0.5% by weight, more preferably 0.01% to 0.1% by weight in the CMP slurry composition. May be included. Within this range, growth of microorganisms such as bacteria or fungi may be prevented without degrading the polishing performance and storage stability of the CMP composition.

The CMP slurry composition may have a pH of 4 to 10, preferably 5 to 9, more preferably 6 to 8. Within this range, the polishing rate of the metal wiring can be increased, and the polishing surface state can be improved.

The CMP slurry composition may further comprise a complexing agent.

The complexing agent serves to complex the copper oxide produced during the polishing of metals, in particular copper. The complexing agent inhibits the re-adsorption of the copper oxide produced by chelate reaction with the copper oxide to the copper film, which is the layer to be polished, increases the polishing rate for the copper film, and reduces surface defects.

The complexing agent may include an organic acid or a salt thereof, an amino acid or a salt thereof, alcohols such as dialcoal, trialcohol, polyalcohol, an amine-containing compound, and the like, which may be included alone or in combination of two or more thereof. Complexing agents include ammonium acetate, ammonium oxalate, ammonium formate, ammonium tartarate, ammonium lactate, glycine, alanine, serine, aspartic acid, glutamic acid, proline, oxyproline, arginine, cystine, histidine, tyrosine, leucine, lysine, methionine, valine, isoleucine , Trionine, tryptophan, phenylalanine, ammonium tetrahydrate, aminobenzotriazole, aminobutyric acid, aminoethylaminoethanol, aminopyridine; Carbonyl compounds and salts thereof, carboxylic acid compounds and salts thereof, such as carboxylic acid compounds containing one or more hydroxyl groups and salts thereof, dicarboxylic acids and salts thereof, tricarboxylic acids and salts thereof, polycarboxylic acids and salts thereof, one or more sulfonic acid groups and (A) A carboxylic acid compound containing a phosphoric acid group, and its salt can be included. Preferably the complexing agent may comprise an amino acid or a salt thereof, more preferably glycine or a salt thereof.

The complexing agent may be included in an amount of 0.01 wt% to 20 wt%, preferably 0.05 wt% to 10 wt%, more preferably 0.1 wt% to 5 wt% in the CMP slurry composition. Within this range, the polishing rate, the dispersion stability of the slurry can be improved, and the surface properties of the copper film can be improved.

The CMP slurry composition may further comprise a corrosion inhibitor.

By including an azole compound as a corrosion inhibitor, dishing, erosion, and the like can be reduced in the polishing target to improve flatness. The azole compound may include one or more of triazole and tetrazole. Preferably, a triazole compound can be used as an azole compound.

Triazoles may use a compound of Formula 4 or Formula 5:

<Formula 4>

(In Formula 4,

R ¹ and R ² each independently represent a hydrogen atom; Unsubstituted alkyl group having 1 to 10 carbon atoms; Unsubstituted aryl group having 6 to 10 carbon atoms; Amino group (-NH ₂ ); An alkyl group having 1 to 10 carbon atoms substituted with a sulfonic acid group, a carboxylic acid group, or an amino group; An aryl group having 6 to 10 carbon atoms substituted with an amino group; An aryl group having 6 to 10 carbon atoms substituted with a carboxylic acid group; Or an aryl group having 6 to 10 carbon atoms substituted with a sulfonic acid group,

R ¹ , R ² may be connected to each other to form an unsubstituted aryl group having 4 to 10 carbon atoms or an aryl group having 4 to 10 carbon atoms substituted,

R ³ is a hydrogen atom or a hydroxyl group). In this case, the substituted means substituted with an alkyl group having 1 to 10 carbon atoms.

<Formula 5>

(In Chemical Formula 5,

R ⁴ and R ⁵ each independently represent a hydrogen atom; Unsubstituted alkyl group having 1 to 10 carbon atoms; Unsubstituted aryl group having 6 to 10 carbon atoms; Amino group (-NH ₂ ); An alkyl group having 1 to 10 carbon atoms substituted with a sulfonic acid group, a carboxylic acid group, or an amino group; An aryl group having 6 to 10 carbon atoms substituted with an amino group; An aryl group having 6 to 10 carbon atoms substituted with a carboxylic acid group; Or an aryl group having 6 to 10 carbon atoms substituted with sulfonic acid groups).

Preferably, the triazole may comprise one or more of 1,2,3-triazole, 1,2,4-triazole. Triazole may also be included in the CMP slurry composition as the triazole itself or as a salt of triazole.

Preservatives may be included in 0.001% to 1% by weight, preferably 0.002% to 0.1% by weight, more preferably 0.005% to 0.05% by weight in the CMP slurry composition. Within this range, the polishing rate can be made high, and the flatness can be improved by lowering dishing and erosion during partial polishing with a pattern.

The CMP slurry composition may further comprise an oxidizing agent.

The oxidant may oxidize the surface of the metal wiring to facilitate polishing, and may even the surface of the metal wiring layer so that the surface roughness is good even after polishing. Oxidizing agents are inorganic peroxides, organic peroxides, bromic acid or salts thereof, nitric acid or salts thereof, chloric acid or salts thereof, chromic acid or salts thereof, iodic acid or salts thereof, iron or salts thereof, copper or salts thereof, rare earth metal oxides , Transition metal oxides, potassium dichromate, and the like. The "peroxide" is a compound containing one or more peroxide groups (-O-O-) or containing elements in the highest oxidation state. For example, the oxidizing agent may be hydrogen peroxide, benzyl peroxide, sodium peroxide, di-t-butyl peroxide, peracetic acid, persulfate, periodic acid, monopersulfuric acid, dipersulfuric acid or It may include one or more of its salts.

The oxidant may be included in 0.01% by weight to 10% by weight, preferably 0.1% by weight to 5% by weight in the CMP slurry composition. In the above range may be excellent polishing performance and step improvement effect.

The CMP slurry composition may further comprise one or more of acids.

The acid may improve the stability of the CMP slurry composition and allow to adjust the pH of the CMP slurry composition. The acid may comprise at least one of inorganic acids and organic acids. The inorganic acid may include, but is not limited to, one or more of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid. The organic acid may include one or more of acetic acid, citric acid, glutaric acid, glycolic acid, formic acid, lactic acid, malic acid, maleic acid, oxalic acid, phthalic acid, succinic acid, tartaric acid.

The inorganic acid may be included in 0.001% to 0.1% by weight, preferably 0.01% to 0.1% by weight, more preferably 0.01% to 0.05% by weight of the CMP Slisley composition. The organic acid may be included in 0.001% to 0.1% by weight, preferably 0.01% to 0.1% by weight, more preferably 0.01% to 0.05% by weight in the CMP slurry composition.

The CMP slurry composition may further comprise a pH adjuster to adjust the pH. pH adjusting agents may include bases such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate and the like. The pH adjusting agent may be included at 0.001% to 1% by weight in the CMP slurry composition.

The CMP slurry composition may further comprise conventional additives such as surfactants, dispersants, modifiers, surfactants, and the like.

The metal wire polishing method of the present invention may include polishing using the CMP slurry composition for metal wire polishing of the present invention.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, it is presented as a preferred example of the present invention and should not be construed as limiting the present invention by any means.

Example  One

(A) As a metal oxide abrasive, silica (FUSO, PL-2, non-spherical) having an average particle diameter of 45 nm, a compound of Formula 1, (B) glycine, and (C) 1H-1,2,3-triazole were mixed. And, the rest of the polar solvent was mixed with deionized water to prepare a CMP slurry composition.

The CMP slurry composition comprises (A) 0.1 wt% metal oxide abrasive, (B) 1.2 wt% glycine, (C) 0.02 wt% 1H-1,2,3-triazole, 0.01 wt% compound of formula 1, 1.0 wt% hydrogen peroxide %, And residual deionized water. The pH of the slurry composition was adjusted to KOH and brought to 7.

Example  2 to Example  9 and Comparative example  One

In Example 1, the CMP slurry composition was prepared in the same manner except for changing the content (wt%) of each component in the CMP slurry composition as shown in Table 1 below.

The microbial contamination area of the slurry compositions prepared in Examples and Comparative Examples was evaluated according to the following method and the results are shown in Table 1 below.

Microbial Contamination Area (Unit: % ) : A mixture of 1,000 g of the slurry composition prepared in Example and Comparative Example was stirred for 2 hours at 2,000 rpm in a 2 L flask using a high pressure dispersion method. The resulting slurry was filtered using a pore size 0.2 μm filter. After contaminating yeast, mold and bacteria with the obtained sample, 0.5 ml of the sample was incubated at 60 ° C. for 5 days in the culture medium Potato Dextrose Agar Medium (3M), and the ratio of the total area of the culture medium to the total area of the culture medium (% ) Was measured.

(A) (B) (C) pH Microbial Contamination Area (%) compound content Example 1 0.1 1.2 0.02 Formula 1 0.01 7 5 Example 2 0.1 1.2 0.02 Formula 1 0.03 7 One Example 3 0.1 1.2 0.02 Formula 1 0.1 7 0 Example 4 0.1 1.2 0.02 Formula 2 0.01 7 2 Example 5 0.1 1.2 0.02 Formula 2 0.03 7 One Example 6 0.1 1.2 0.02 Formula 2 0.1 7 0 Example 7 0.1 1.2 0.02 Formula 3 0.01 7 3 Example 8 0.1 1.2 0.02 Formula 3 0.03 7 2 Example 9 0.1 1.2 0.02 Formula 3 0.1 7 0 Comparative Example 1 0.1 1.2 0.02 - - 7 39

* In Table 1

Formula 1: Solvay

Formula 2: Aldrich

Formula 3: Aldrich

As shown in Table 1, the CMP slurry composition of the present invention has a small microbial contamination area, high storage stability of the CMP slurry composition, prevents agglomeration of metal oxide abrasives, prevents a decrease in polishing performance, and The processability of the semiconductor manufacturing process was improved by avoiding filter clogging during filtration.

On the other hand, Comparative Example 1, which does not include at least one compound of Formula 1, Formula 2, or Formula 3 of the present invention, had a severe propagation of microorganisms.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (7)

At least one of a polar solvent and a nonpolar solvent; Metal oxide abrasives; And at least one compound represented by Formula 1, Formula 2, and Formula 3 below:
<Formula 1>

<Formula 2>

<Formula 3>

.
The CMP slurry composition of claim 1, wherein at least one compound of Formula 1, Formula 2, and Formula 3 is included in an amount of 0.001% by weight to 1% by weight in the CMP slurry composition.
The CMP slurry composition of claim 1, wherein the CMP slurry composition has a pH of 4 to 10.
The CMP slurry composition of claim 1, wherein the CMP slurry composition further comprises an amino acid or a salt thereof.
The CMP slurry composition of claim 4, wherein the amino acid is glycine.
The CMP slurry composition of claim 1, wherein the CMP slurry composition further comprises at least one of triazole and tetrazole.
The metal wiring polishing method using the CMP slurry composition for metal wiring polishing of any one of Claims 1-6.