TWI782890B - Chemical mechanical polishing (cmp) composition, process for the manufacture of a semiconductor device by using the same, and the use of the composition for polishing of cobalt and/or cobalt alloy comprising substrates - Google Patents

Abstract

Use of a chemical mechanical polishing (CMP) composition (Q) for chemical mechanical polishing of a substrate (S) comprising (i) cobalt and/or (ii) a cobalt alloy, wherein the CMP composition (Q) comprises (A) Inorganic particles (B) an anionic surfactant of the general formula (I) R-S (I) wherein R is C₅-C₂₀-alkyl, C₅-C₂₀-alkenyl, C₅-C₂₀-alkylacyl or C₅-C₂₀-alkenylacyl and S is a sulfonic acid derivative, an amino acid derivative or a phosphoric acid derivative or salts or mixtures thereof (C) at least one amino acid, (D) at least one oxidizer (E) an aqueous medium and wherein the CMP composition (Q) has a pH of from 7 to 10.

Description

Chemical Mechanical Polishing (CMP) Composition, Method for Manufacturing Semiconductor Devices by Using the Composition, and Use of the Composition in Polishing a Substrate Containing Cobalt and/or Cobalt Alloy

The present invention basically relates to a chemical method for grinding substrates for the semiconductor industry containing cobalt and/or cobalt alloys, containing inorganic particles, anionic surfactants as corrosion inhibitors, at least one amino acid, at least one oxidizing agent and an aqueous medium Use of mechanically milled (CMP) compositions. The invention also relates to a method for manufacturing a semiconductor device comprising chemical mechanical polishing of a substrate or layer in the presence of the chemical mechanical polishing (CMP) composition. The CMP composition exhibits improved and tunable etching behavior and good grinding performance relative to cobalt and/or cobalt alloys.

In the semiconductor industry, chemical mechanical polishing (abbreviated CMP) is a well-known technique applied in the fabrication of advanced photonic, microelectromechanical, and microelectronic materials and devices, such as semiconductor wafers.

During the manufacture of materials and devices used in the semiconductor industry, CMP is used to Planarizes metal and/or oxide surfaces. CMP uses the interaction of chemical and mechanical action to achieve the flatness of the surface to be polished. The chemistry is provided by a chemical composition, also known as a CMP composition or CMP slurry. The mechanical action is usually performed by means of a grinding pad, which is typically pressed onto the surface to be ground and mounted on a moving platen. The movement of the platen is usually linear, rotary or orbital.

In a typical CMP method step, the wafer holder is rotated to bring the wafer to be polished into contact with the polishing pad. The CMP composition is usually applied between the wafer to be polished and the polishing pad.

With the continuous shrinking of feature sizes in Ultra Large Scale Integrated Circuit (ULSI) technology, the size of copper interconnect structures has become smaller and smaller. To reduce the RC delay, the thickness of the barrier layer or adhesive layer in the copper interconnection structure becomes thinner. Traditional copper barrier/adhesion layer stack Ta/TaN is no longer suitable because the resistivity of Ta is relatively high and copper cannot be plated directly on Ta. Cobalt has lower resistivity and is cheaper than Ta. Adhesion between Cu and Co is good. Cu can easily nucleate on Co, and copper can also be directly plated on cobalt.

In integrated circuits, Co is used as an adhesion layer or barrier layer for copper interconnects, while Co can also be used as nanocrystalline Co in memory devices and as a metal gate in MOSFETs.

Porous low-k dielectric materials have been used in current interconnect structures. It has been reported that low-k materials can be easily damaged by plasma or abrasive slurries. In the current chemical mechanical polishing process, in order to reduce the damage to the low-k dielectric, most current slurries used for copper and barrier ribs are acidic. However, it was observed that copper and cobalt are susceptible to dissolution in acidic solutions containing oxidizing agents such as hydrogen peroxide. This makes the grinding rate of copper and cobalt so high that it will induce dishing of the copper wire. Additionally, the dissolution of the cobalt adhesion layer on the sidewalls of the copper interconnect structure may cause delamination of the copper lines and cause safety concerns.

Depending on the integration scheme used in Ultra Large Scale Integration (ULSI) technology, Co-existence of Co, Cu, and low-k dielectric materials in varying amounts and layer thicknesses presents several challenges to compositions for chemical mechanical polishing in semiconductor device fabrication in terms of selectivity, etch, removal rate, and surface quality.

In the state of the art, the use of CMP compositions containing inorganic particles, anionic surfactants, amino acids, oxidizing agents and aqueous media for grinding substrates for the semiconductor industry is known and described eg in the following references.

US 8 506 359 B2 discloses a chemical mechanical polishing aqueous dispersion, which contains silica particles (A); amino acid (B2), which is selected from the group consisting of glycine, alanine and histidine, and further contains organic An acid, the organic acid contains a nitrogen-containing heterocycle and a carboxyl group; and an anionic surfactant (C2), which includes at least one functional group selected from the group consisting of carboxyl, sulfonic acid, and phosphoric acid. The aqueous dispersion is used for chemical mechanical polishing of a polishing target surface of a semiconductor device containing at least one of the following: a metal film; a barrier metal film; and an insulating film with a pH of 6-12.

Therefore, there would be a high need to use CMP compositions and CMP methods that can avoid all the disadvantages associated with the prior art, such as low material removal rate of Co, high Co corrosion, acidic pH, need for separate corrosion inhibitors and no abrasive performance the ability to adjust.

One of the objects of the present invention is to provide substrates suitable for chemical mechanical grinding containing cobalt and/or cobalt alloys and showing improved grinding performance, in particular low corrosion of cobalt and/or cobalt alloys and durability of cobalt and/or cobalt alloys Use of CMP compositions with controlled and adjustable material removal rates. Additionally, the use of CMP compositions is sought that yields high material removal rates for cobalt and/or cobalt alloys, is compatible with low-k dielectric materials and other metals (such as copper for semiconductor substrates), yields high quality surfaces Smooth finish, less dishing, storage stable and will be ready to go in neutral to alkaline pH range use.

In addition, individual CMP methods will be provided.

Silica Penetrating Thus, the present invention describes the use of a chemical mechanical polishing (CMP) composition (Q) for chemical mechanical polishing of a substrate (S) containing (i) cobalt and/or (ii) cobalt alloys, wherein The CMP composition (Q) contains (A) inorganic particles (B) anionic surfactant R-S (I) of general formula (I)

Wherein R is C ₅ -C ₂₀ alkyl, C ₅ -C ₂₀ alkenyl, C ₅ -C ₂₀ alkyl acyl or C ₅ -C ₂₀ alkenyl acyl and S is a sulfonic acid derivative, an amino acid derivative or phosphoric acid derivatives or their salts or mixtures (C) at least one amino acid, (D) at least one oxidizing agent (E) aqueous medium, and wherein the pH of the CMP composition (Q) is 7 to 10.

According to another aspect of the present invention, there is provided a chemical mechanical polishing (CMP) composition, which contains (A) colloidal silica particles, the total amount of which is based on the total weight of each CMP composition is 0.01wt% to 3 wt % (B) of at least one anionic surfactant (B) selected from N-oleyl sarcosine, N-lauroyl sarcosine, N-cocoyl sarcosine, 4-dodecyl sarcosine The group consisting of alkylbenzenesulfonic acid, N-cocoyl glutamate and C ₆ -C ₁₀ alkyl phosphate, the total amount of which is 0,001 wt% to 0, based on the total weight of the respective CMP composition, 09wt% (C) At least one amino acid (C) selected from the group consisting of glycine, alanine, leucine, valine, cysteine, serine and proline or their salts , the total amount of which is 0,2 wt% to 0,9 wt% based on the total weight of the respective CMP composition (D) hydrogen peroxide, the total amount of which is 0,2 wt% to the total weight of the respective CMP composition 2wt%, (E) aqueous medium, wherein the pH of the CMP composition (Q) is 7-10.

It achieves the object of the present invention.

Furthermore, the above objects of the present invention are achieved by a method for manufacturing semiconductor devices comprising chemical mechanical polishing (CMP) of substrates (S) used in the semiconductor industry in the presence of said chemical mechanical polishing (CMP) composition (Q), Wherein the substrate (S) contains (i) cobalt and/or (ii) cobalt alloy.

Surprisingly, it has been found that the use of the CMP compositions (Q) according to the invention results in a combination of improved corrosion inhibition and high cobalt material removal rates for substrates containing cobalt and/or cobalt alloys.

Preferred embodiments are explained in the claims and specification. It should be understood that combinations of preferred embodiments are within the scope of the invention.

According to the present invention, the CMP composition contains inorganic particles (A).

In general, the chemical properties of the inorganic particles (A) are not particularly limited. (A) may have the same chemical nature or be a mixture of particles of different chemical nature. As a general rule, particles (A) having the same chemical nature are preferred.

(A) may be - inorganic particles, such as metals, metal oxides or carbides, including metalloids, metalloid oxides or carbides, or - a mixture of inorganic particles.

In general, (A) may be - a colloidal inorganic particle - a fume-like inorganic particle, - a mixture of different types of colloidal and/or fume-like inorganic particles.

In general, colloidal inorganic particles are inorganic particles prepared by wet precipitation; fume-like inorganic particles are prepared by hydrolyzing, for example, metal chloride precursors with high-temperature flames of hydrogen in the presence of oxygen, for example using the Aerosil ^® method.

Preferably, the inorganic particles (A) are colloidal inorganic particles or smoke-like inorganic particles or a mixture thereof. Among them, oxides and carbides of metals or metalloids are preferred. More preferably, the particles (A) are aluminum oxide, cerium oxide, copper oxide, iron oxide, nickel oxide, manganese oxide, silica, silicon nitride, silicon carbide, tin oxide, titanium dioxide, titanium carbide, tungsten oxide, oxide Yttrium, zirconia or mixtures or composites thereof. Optimally, the particles (A) are alumina, ceria, silica, titania, zirconia or mixtures or composites thereof. Specifically, (A) is silica particles. For example, (A) is colloidal silica particles.

As used herein, the term "colloidal silica" refers to silica that has been prepared by condensation polymerization of Si(OH) ₄ . Precursor Si(OH) ₄ can be obtained, for example, by hydrolysis of high-purity alkoxysilanes or by acidification of aqueous silicate solutions. Such colloidal silica can be prepared according to U.S. Patent No. 5,230,833 or can be obtained as any of various commercial products, such as Fuso PL-1, PL-2 and PL-3 products, and Nalco 1050, 2327 and 2329 products, and other similar products commercially available from DuPont, Bayer, Applied Research, Nissan Chemical, Nyacol, and Clariant.

According to the present invention, the amount of (A) in the CMP composition (Q) is not more than 3.0 wt% based on the total weight of the composition (Q). Based on the total weight of the composition (Q), it is preferably not more than 2.5wt%, most preferably not more than 1.8wt%, especially not more than 1.5wt%. According to the present invention, the amount of (A) is at least 0.0001 wt%, preferably at least 0.02 wt%, more preferably at least 0.1 wt%, most preferably at least 0.2 wt%, especially at least 0.3 wt%, based on the total weight of the composition (Q) %. For example, the amount of (A) may range from 0.4 wt% to 1.2 wt%.

In general, the particles (A) can be included in the composition (Q) in various particle size distributions. The particle size distribution of the particles (A) may be unimodal or multimodal. In the case of multimodal particle size distributions, bimodal is generally preferred. In order to have an easily reproducible characteristic profile and easy reproducible conditions during the CMP process of the invention, a monomodal particle size distribution of the particles (A) may be preferred. It is generally optimal for particles (A) to have a monomodal particle size distribution.

In general, what particle size distribution the particles (A) may have is not particularly limited.

The average particle size of the particles (A) can vary within a wide range. The average particle size is the d ₅₀ value of the particle size distribution of the particles (A) in the aqueous medium (E) and can be measured eg using dynamic light scattering (DLS) or static light scattering (SLS) methods. These methods and others are well known in the art, see for example Kuntzsch, Kuntzsch, Timo; Witnik, Ulrike; Hollatz, Michael Stintz; Ripperger, Siegfried; Characterization of Slurries Used for Chemical-Mechanical Polishing (CMP) in the Semiconductor Industry ; Chem. Eng. Technol; 26 (2003), Vol. 12, p. 1235.

For DLS typically a Horiba LB-550 V (DLS, dynamic light scattering measurement according to manual) or any other such instrument is used. This technique is used in particle scattering laser light sources (λ= 650 nm) to measure the hydrodynamic diameter of the particle, which is detected at an angle of 90° or 173° to the incident light. Changes in scattered light intensity are attributed to random Brownian motion of the particles as they move through the incident beam and are monitored over time. The decay constant is extracted using an autocorrelation function performed by the instrument as a function of delay time; smaller particles move through the incident beam at higher speeds and correspond to faster decays.

These decay constants are proportional to the particle's diffusion coefficient _Dt and are used to calculate the particle size according to the Stokes-Einstein equation:

It is assumed therein that the suspended particles (1) have a spherical morphology and (2) are uniformly dispersed (ie not agglomerated) throughout the aqueous medium (E). This relationship is expected to hold for particle dispersions containing less than 1% by weight of solids, since there is no significant deviation in the viscosity of the aqueous dispersion (E), where η = 0.96 mPa. s (at T=22°C). The particle size distribution of the smoky or colloidal inorganic particle dispersion (A) is usually measured in a plastic optical cell at a solid concentration of 0.1% to 1.0%, and diluted with a dispersion medium or ultrapure water if necessary.

Preferably, the average particle size of the particles (A) is in the range of 20nm to 200nm as measured by dynamic light scattering technique using an instrument such as a High Performance Particle Sizer (HPPS) or Horiba LB550 from Malvern Instruments Ltd. Within, more preferably in the range of 25nm to 180nm, most preferably in the range of 30nm to 170nm, especially preferably in the range of 40nm to 160nm, and especially in the range of 45nm to 150nm.

The BET surface of the particles (A), determined according to DIN ISO 9277:2010-09, can vary within a wide range. Preferably, the BET surface of particles (A) is in the range of 1 to 500 m ² /g, more preferably in the range of 5 to 250 m ² /g, most preferably in the range of 10 to 100 m ² /g, especially in the range of 20 to 95 In the range of m ² /g, for example, in the range of 25 to 92 m ² /g.

Particles (A) may have various shapes. Thus, particles (A) may have one or substantially only one type of shape. However, it is also possible for the particles (A) to have different shapes. For example, there may be two types of particles (A) of different shapes. For example, (A) may have the following shapes: agglomerates, cubes, cubes with hypotenuses, octahedrons, icosahedrons, cocoons, nodules, and with or without protrusions or indentations. sphere. Preferably, the particles are substantially spherical, whereby they typically have protrusions or indentations.

It may be preferable that the inorganic particles (A) are cocoon-like. Cocoons may or may not have protrusions or indentations. Cocoon-like particles are particles with a short axis of 10 nm to 200 nm and a long axis/short axis ratio of 1.4 to 2.2, more preferably 1.6 to 2.0. Its average shape factor is preferably 0.7 to 0.97, more preferably 0.77 to 0.92, the average sphericity is preferably 0.4 to 0.9, more preferably 0.5 to 0.7, and the average equivalent circle diameter is preferably 41nm to 66nm, more preferably 48nm to 60 nm, which can be determined by transmission electron microscopy and scanning electron microscopy.

The determination of the shape factor, sphericity and circle-equivalent diameter of cocoon-like particles is explained below with reference to FIGS. 1 to 4 .

The shape factor obtains information about the shape and indentation of individual particles (see Figure 1) and can be calculated according to the following formula: shape factor = 4π(area/perimeter2 ⁾

Spherical particles without indentations have a shape factor of 1. The value of the form factor decreases as the number of dimples increases.

Sphericity (see Figure 2) uses the moment about the mean to obtain information about the elongation of individual particles and can be calculated according to the following formula, where M is the center of gravity of the individual particle: Sphericity = (M _xx - M _yy )-[4 M _xy ² +(M _yy -M _xx ) ² ] ^0.5 /(M _xx -M _yy )+[4 M _xy ² +(M _yy -M _xx ) ² ] ^0.5 elongation=(1/ball degrees) ^0.5

in

Mxx=Σ(xx _average ) ² /N

Myy=Σ(yy _average ) ² /N

Mxy=Σ[(xx _average )×(yy _average )]/N

N is the number of pixels forming the image of the respective particle

x,y pixel coordinates

xaverage The _average of the x-coordinates of the N pixels that form the image of the particle

yaverage The _average value of the y coordinates of the N pixels that form the image of the particle

The spherical particle has a sphericity of 1. The value of sphericity decreases as the particle elongates.

The equivalent circular diameter (hereinafter also abbreviated as ECD) of individual non-circular particles obtains information about the diameter of a circle having the same area as the respective non-circular particle (see FIG. 3 ).

The mean shape factor, mean sphericity and mean ECD are the arithmetic mean of the individual properties related to the number of particles analyzed.

The procedure for particle shape identification is as follows. An aqueous cocoon-like silica particle dispersion having a solids content of 20 wt % was dispersed on a carbon foil and dried. Dried dispersions were analyzed by using energy filtration-transmission electron microscopy (EF-TEM) (120 kV) and scanning electron microscopy secondary electron imaging (SEM-SE) (5 kV). EF-TEM images with a resolution of 2k, 16 bit, 0.6851 nm/pixel (see Figure 4) were used for this analysis. The image is binary encoded using a threshold after noise suppression. The particles were then separated manually. distinguish overlying particles from edge particles, and the Isoparticles were not used for analysis. ECD, shape factor and sphericity as previously defined were calculated and statistically classified.

For example, the cocoon-like particles may be FUSO ^® PL-3 manufactured by Fuso Chemical Corporation with an average primary particle diameter (d1) of 35 nm and an average secondary particle diameter (d2) of 70 nm.

According to the present invention, used CMP composition (Q) contains the anionic surfactant R-S (I) of (B) general formula (I)

R may preferably be C ₅ -C ₂₀ alkyl, C ₅ -C ₂₀ alkenyl having at least one carbon-carbon double bond, C ₅ -C ₂₀ alkyl acyl or C ₅ -C ₂₀ alkenyl acyl, more Preferred R can be hexyl, heptyl, octyl, nonyl, decyl, hexenyl, heptenyl, octenyl, nonyl, decenyl, undecenyl, dodecenyl, oleyl , lauryl or cocoyl, the best R can be hexyl, heptyl, octyl, nonyl, decyl, hexenyl, octenyl, decenyl, dodecenyl, oleyl, Lauryl or cocoyl, especially preferably R can be hexyl, oleyl, lauryl or cocoyl.

S may preferably be a sulfonic acid derivative, an amino acid derivative or a phosphoric acid derivative or a salt thereof, more preferably S may be sulfonic acid, benzenesulfonic acid, sarcosine, glutamic acid, phosphoric acid or monophosphate or its Salt, the best S can be sulfonic acid, sarcosine, sarcosine, glutamic acid or phosphoric acid or a salt thereof, especially preferably S can be benzenesulfonic acid, sarcosine, glutamic acid or phosphoric acid or a salt thereof, R and S are linked together by chemical bonds, for example by forming amides, phosphates, sulfonates or substituted benzenesulfonic acids.

These anionic surfactants may be used alone or in combination or in the form of their salts.

For example, the compound (B) of general formula (I) can be N-oleyl sarcosine, N-lauroyl sarcosine, N-cocoyl sarcosine, 4-dodecylbenzenesulfonic acid, N-cocoyl glutamate or hexyl phosphate, as defined above Compound (B) of formula (I) acts alone as a corrosion inhibitor for cobalt and/or cobalt alloys without the addition of commonly known corrosion inhibitors used in CMP, such as benzotriazole (BTA). It is currently believed that compound (B) of general formula (I) can act as a corrosion inhibitor by forming a protective molecular layer on the surface of cobalt and/or cobalt alloys. Surprisingly, it has now been found that, contrary to the known and commonly used compound benzotriazole (BTA) and derivatives of BTA and other triazoles used in CMP compositions in the prior art, the compound (B) of general formula (I) There is an advantageous effect on lower etch rates for cobalt and/or cobalt alloys, thus better corrosion inhibition and higher material removal rates for substrates containing cobalt and/or cobalt alloys.

According to the present invention, the amount of (B) in the CMP composition (Q) used is not more than 0.09 wt% based on the total weight of the composition (Q). Based on the total weight of the composition (Q), it is preferably not more than 0.085wt%, most preferably not more than 0.08wt%, especially not more than 0.06wt%. According to the present invention, the amount of (B) is at least 0.001 wt%, preferably at least 0.0025 wt%, more preferably at least 0.005 wt%, most preferably at least 0.007 wt%, especially at least 0.008 wt%, based on the total weight of the composition (Q) %. For example, the amount of (B) may range from 0.009 wt% to 0.05 wt%.

According to the invention, the CMP composition used contains at least one amino acid (C).

In general, organic compounds with amine groups and acid groups are called amino acids. For the purposes of the present invention, all individual stereoisomers and their racemic mixtures are also considered amino acids. Preferably, both amine and acid groups are attached to one carbon (known as alpha-aminocarboxylic acids) for use as chemical additives in CMP slurries. Many α-aminocarboxylic acids are known, and there are twenty "natural" amino acids that serve as building blocks of proteins in living organisms. Amino acids depend on their aqueous carrier Depending on the side chains present, they can be hydrophilic, neutral or hydrophobic. The addition of alpha amino acids as grinding additives increases the metal material removal rate.

At least one α-amino acid (C) can be represented by the general formula (II) H ₂ N-CR ¹ R ² COOH (II)

wherein R and R are independently ^hydrogen , unsubstituted or substituted with ^one or more substituents selected from the group consisting of cyclic, branched and linear moieties having 1 to 8 carbon atoms: Nitrogen substituents, oxygen-containing substituents, and sulfur-containing substituents include, but are not limited to, -COOH, -CONH ₂ , -NH ₂ , -S-, -OH, -SH, and mixtures and salts thereof.

Preferably, at least one amino acid (C) is α-alanine, arginine, cystine, cysteine, glutamine, glycine, histidine, isoleucine, leucine Amino acid, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine and their mixtures and salts. More preferably (C) is α-alanine, arginine, glycine, histidine, leucine, lysine, proline, serine, valine and mixtures and salts thereof. Most preferably (C) is α-alanine, glycine, proline, serine and mixtures and salts thereof, especially (C) is α-alanine, serine, glycine and mixtures thereof and Salts, eg (C) is glycine.

According to the present invention, the amount of amino acid (C) in the CMP composition (Q) is not more than 2.25wt% based on the total weight of the composition (Q). Based on the total weight of the composition (Q), it is more preferably not more than 1.2 wt%, most preferably not more than 1 wt%, especially not more than 0.8 wt%. According to the invention, the amount of (C) is at least 0.1% by weight, based on the total weight of the composition (Q). Based on the total weight of the composition (Q), it is preferably at least 0.3 wt%, more preferably at least 0.4 wt%, most preferably at least 0.5 wt%, especially at least 0.6 wt%. For example, the amount of (C) may range from 0.65 wt% to 0,78 wt%.

The CMP composition used according to the invention contains at least one oxidizing agent (D), One to two types of oxidizing agent (D) are preferred, and one type of oxidizing agent (D) is more preferred. Oxidizing agent (D) is different from components (A), (B), (C) and (E). In general, an oxidizing agent is a compound capable of oxidizing the substrate to be polished or one of its layers. Preferably, (D) is a passing oxidizing agent. More preferably, (D) is peroxide, persulfate, perchlorate, perbromate, periodate, permanganate or derivatives thereof. Optimally, (D) is a peroxide or persulfate. In particular, (D) is a peroxide. For example, (D) is hydrogen peroxide.

At least one oxidizing agent (D) may be included in varying amounts in the CMP composition used according to the invention. Preferably, in each case based on the total weight of the CMP composition used according to the present invention, the amount of (D) is not more than 4wt% (wt% means "weight percent" in each case, more preferably not more than 2.5wt% %, preferably not more than 1.8wt%, especially not more than 1.5wt%, for example, not more than 1.2wt%.In each case based on the total weight of the composition used according to the present invention, preferably, (D) The amount is at least 0.2 wt%, better at least 0.25 wt%, optimally at least 0.3 wt%, especially at least 0.35 wt%, for example, at least 0.4 wt%. If hydrogen peroxide is used as oxidizing agent (D), then in each case Based on the total weight of the CMP composition used in the present invention, the amount of (D) is preferably 0.2wt% to 2.8wt%, more preferably 0.28wt% to 1.9wt%, for example, 1.0wt%.

According to the invention, the CMP composition used contains an aqueous medium (E).

(E) can be one type of aqueous medium or a mixture of different types of aqueous medium.

In general, the aqueous medium (E) can be any medium comprising water. Preferably, the aqueous medium (E) is a mixture of water and a water-miscible organic solvent such as alcohol, preferably a C ₁ to C ₃ alcohol, or an alkanediol derivative. More preferably, the aqueous medium (E) is water. Optimally, the aqueous medium (E) is deionized water.

If the total amount of components other than (E) is x% by weight of the CMP composition, the amount of (E) is (100−x)% by weight of the CMP composition (Q).

The properties of the respective CMP compositions used according to the invention, such as the stability of the composition compared to different materials (eg metals versus silica), grinding performance and etching behavior, may depend on the pH of the corresponding composition.

According to the invention, the pH of the CMP composition (Q) used is in the range from 7 to 10. Preferably, the pH values of the compositions used according to the invention are in the range of 7.2 to 9.4, more preferably 7.5 to 9.0, most preferably 7.7 to 8.8, especially preferably 7.8 to 8.6 (eg 7.9 to 8.4).

The CMP composition of the invention used may further optionally comprise at least one additional complexing agent (G), eg one complexing agent, different from the at least one amino acid (C). In general, a complexing agent is a compound capable of complexing ions of the substrate to be polished or one of the layers of the substrate to be polished. Preferably, (G) is a carboxylic acid, N-containing carboxylic acid, N-containing sulfonic acid, N-containing sulfuric acid, N-containing phosphonic acid, N-containing phosphoric acid, or a salt thereof, having at least one COOH group. More preferably, (G) is a carboxylic acid having at least two COOH groups, an N-containing carboxylic acid or a salt thereof. For example, at least one additional complexing agent (G) may be acetic acid, gluconic acid, lactic acid, nitriloacetic acid, ethylenediaminetetraacetic acid (EDTA), imino-di-succinic acid, glutaric acid, citric acid , malonic acid, 1,2,3,4-butanetetracarboxylic acid, fumaric acid, tartaric acid, succinic acid and phytic acid.

Complexing agents (G), if present, may be included in varying amounts. Preferably, the amount of (G) is not more than 20wt%, more preferably not more than 10wt%, most preferably not more than 5wt%, such as not more than 2wt%, based on the total weight of the corresponding composition. Preferably, the amount of (G) is at least 0.05 wt%, more preferably at least 0.1 wt%, most preferably at least 0.5 wt%, for example, at least 1 wt%, based on the total weight of the corresponding composition.

The CMP composition of the present invention used may further optionally comprise at least one biocidal Agent (H), for example, a biocide. In general, a biocide is a compound that deters, renders harmless, or exerts control over any harmful organism by chemical or biological means. Preferably, (H) is a quaternary ammonium compound, an isothiazolinone-based compound, an N-substituted diazene dioxide or an N'-hydroxy-diazene oxide salt. More preferably, (H) is N-substituted diazonium dioxide or N'-hydroxy-diazonium oxide salt.

If present, biocide (H) may be included in varying amounts. If present, the amount of (H) is preferably not more than 0.5wt%, more preferably not more than 0.1wt%, most preferably not more than 0.05wt%, especially not more than 0.02wt%, for example not more than 0.008 wt%. If present, the amount of (H) is preferably at least 0.0001 wt%, more preferably at least 0.0005 wt%, most preferably at least 0.001 wt%, especially at least 0.003 wt%, such as 0.006 wt%, based on the total weight of the corresponding composition.

Depending on the specific requirements of the intended use of the CMP composition used according to the invention, the CMP composition may also contain various other additives, if desired, respectively, including (but not limited to) pH regulators, buffer substances, stabilizers, Surfactants (which may be anionic, nonionic or cationic), friction reducers, and the like. Such other additives are, for example, additives commonly used in CMP compositions and thus known to those skilled in the art. This addition can, for example, stabilize the dispersion, or improve the grinding performance or the selectivity between the different layers.

If present, this additive can be included in varying amounts. Preferably, the amount of the additive is not more than 10wt%, more preferably not more than 1wt%, most preferably not more than 0.1wt%, such as not more than 0.01wt%, based on the total weight of the corresponding composition. Preferably, the amount of the additive is at least 0.0001 wt%, more preferably at least 0.001 wt%, most preferably at least 0.01 wt%, such as at least 0.1 wt%, based on the total weight of the corresponding composition.

The CMP composition (Q) used according to the invention is used for chemical mechanical polishing Substrates (S) containing cobalt and/or cobalt alloys used in the conductor industry.

Cobalt and/or cobalt alloys may be of any type, form or shape. Cobalt and/or cobalt alloys preferably have the shape of layers and/or overgrowth. If the cobalt and/or cobalt alloy has the shape of a layer and/or overgrowth, the content of the cobalt and/or cobalt alloy is preferably greater than 90%, more preferably greater than 95%, and most preferably greater than 95% by weight of the corresponding layer and/or overgrowth. Preferably greater than 98%, especially greater than 99%, such as greater than 99.9%. The cobalt and/or cobalt alloys have preferably been filled or grown in trenches or plugs between other substrates, more preferably in dielectric materials such as _SiO2 , silicon, low-k (BD1, BD2) or ultra-low-k materials) or other separation and filling or growth in trenches or plugs in semiconductor materials used in the semiconductor industry. For example, in the Through Silicon Vias (TSV) intermediate process, after the TSVs are revealed from the backside of the wafer, separation materials such as polymers, photoresists, and/or polyimides can be used for isolation/separation properties. It is used as an insulating material between the subsequent processing steps of wet etching and CMP. There may be a thin layer of barrier material between the included copper and the dielectric material. In general, the barrier material to prevent metal ions from diffusing into the dielectric material can be, for example, Ti/TiN, Ta/TaN, or Ru or Ru alloys, Co or Co alloys.

If the CMP composition (Q) according to the present invention is used for grinding substrates containing cobalt and/or cobalt alloys, the static etch rate (SER) of cobalt is preferably less than 100 Å/min, more preferably less than 80 Å/min, most preferably less than 70Å/min, especially preferably less than 60Å/min, for example, the static etching rate may be less than 38Å/min.

If the CMP composition (Q) according to the present invention is used for grinding substrates containing cobalt and/or cobalt alloys, the material removal rate (MRR) of cobalt is preferably in the range of 300 Å/min to 7500 Å/min, more preferably between In the range of 850Å/min to 6500Å/min, preferably in the range of 900Å/min to 6300Å/min, especially preferably in the range of 920Å/min to 6150Å/min, such as cobalt materials The removal rate is in the range of 930Å/min to 6100Å/min.

A semiconductor device can be manufactured by a method comprising chemical mechanical polishing of a substrate (S) used in the semiconductor industry in the presence of the CMP composition (Q) of the present invention. According to the invention, the method comprises chemical mechanical grinding of the substrate (S) comprising cobalt and/or cobalt alloys.

In general, semiconductor devices that can be manufactured by the method according to the present invention are not particularly limited. Thus, a semiconductor device may be an electronic component that includes semiconductor materials, such as silicon, germanium, and III-V materials. Semiconductor devices may be those devices fabricated as a single discrete device or those devices fabricated as an integrated circuit (IC) consisting of multiple devices fabricated and interconnected on a wafer. The semiconductor device can be a two-terminal device (such as a diode), a three-terminal device (such as a bipolar transistor), a four-terminal device (such as a Hall effect sensor), or a multi-terminal device. Preferably, the semiconductor device is a multi-terminal device. The multi-terminal device may be a logic device such as an integrated circuit and a microprocessor or a memory device such as random access memory (RAM), read only memory (ROM) and phase change random access memory (PCRAM). Preferably, the semiconductor device is a multi-terminal logic device. Specifically, the semiconductor device is an integrated circuit or a microprocessor.

Generally, in integrated circuits, Co is used as an adhesion or barrier layer for copper interconnects. In the nanocrystalline form of Co, Co is included, for example, in memory devices and as the metal gate in MOSFETs. Cobalt can also be used as a seed to achieve copper plating by electrodeposition. Cobalt or cobalt alloys can also replace copper for wiring in one or more layers. For example, capacitors (CAP) can be formed from metal, insulator, metal (MIM) and thin film resistors in successive layers at the same level. Circuit designers can now wire TaN thin film resistors down to the lowest metal level, which reduces parasitics and allows more efficient use of existing wiring levels. Excess copper and/or cobalt and pastes containing Co in the form of, for example, metal nitrides or metal carbonitrides such as Co/TaN, Co/TiN, Co/TaCN, Co/TiCN Composite/barrier layers or, for example, a single cobalt alloy layer such as CoMo, CoTa, CoTi and CoW above the dielectric can be removed by chemical mechanical polishing methods according to the present invention.

In general, the cobalt and/or cobalt alloys can be prepared or obtained in different ways. Cobalt or cobalt alloys can be produced by ALD, PVD or CVD methods. It is possible that cobalt or a cobalt alloy is deposited onto the barrier material. Suitable materials for barrier applications are well known in the art. The barrier prevents the diffusion of metallic atoms or ionic cobalt or copper into the dielectric layer and improves the adhesion properties of the conductive layer. Ta/TaN, Ti/TiN can be used.

In general, such cobalt and/or cobalt alloys can be of any type, form or shape. The cobalt and/or cobalt alloy preferably has a layered and/or overgrown shape. If the cobalt and/or cobalt alloy has the shape of a layer and/or overgrowth, the content of the cobalt and/or cobalt alloy is preferably greater than 90%, more preferably greater than 95%, and most preferably greater than 95% by weight of the corresponding layer and/or overgrowth. Preferably greater than 98%, especially greater than 99%, such as greater than 99.9%. This cobalt and/or cobalt alloy has preferably been filled or grown in trenches or plugs between other substrates, preferably in dielectric materials such as _SiO2 , silicon, low-k (BD1, BD2) or ultra-low-k materials) or other separation and filling or growth in trenches or plugs in semiconductor materials used in the semiconductor industry.

In general, downward pressure or force is the downward pressure or force applied by the carrier to the wafer against the pad during CMP. This downward pressure or force can be measured, for example, in pounds per square inch (abbreviated psi).

For example, the method of the present invention can be performed at a down pressure of 2 psi or less. Preferably, the downward pressure is in the range of 0.1psi to 1.9psi, more preferably in the range of 0.3psi to 1.8psi, most preferably in the range of 0.4psi to 1.7psi, especially preferably in the range of 0.8psi to 1.6psi, For example 1.3psi.

If the method of the present invention contains chemical mechanical grinding of substrates containing cobalt and/or cobalt alloys, the static etch rate (SER) of cobalt is preferably less than 100 Å/min, more preferably less than 80 Å/min, most preferably less than 70 Å/min, especially higher Preferably less than 60Å/min, for example, the static etch rate may be less than 38Å/min.

If the method of the present invention includes chemical mechanical grinding of substrates containing cobalt and/or cobalt alloys, the cobalt material removal rate (MRR) is preferably in the range of 300 Å/min to 7500 Å/min, more preferably 850 Å/min to 6500 Å/min min range, preferably in the range of 900Å/min to 6300Å/min, especially preferably in the range of 920Å/min to 6150Å/min, for example, the cobalt material removal rate is in the range of 930Å/min to 6100Å/min.

These different ranges of cobalt material removal rates can be achieved, for example, by varying the concentration of component (B) of the CMP composition (Q) and the concentration of abrasive (A).

Examples of CMP compositions (Q) used according to the invention

Z1:

(A) colloidal silica particles, the total amount of which is 0,01 wt% to 1.8 wt% based on the total weight of the respective CMP composition (B) N-oleyl sarcosine, the total amount of which is represented by the respective The total weight of the CMP composition is 0,008 wt% to 0,08 wt% (C) at least one amino acid (C) selected from the group consisting of glycine, alanine, leucine, valine, cysteine , serine and proline or their salts, the total amount of which is based on the total weight of the respective CMP composition is 0,35wt% to 0,8wt% (D) hydrogen peroxide, the total amount of which is each The total weight of other CMP composition is 0,2wt% to 1.5wt%, (E) an aqueous medium, wherein the pH of the CMP composition (Q) is 7.8 to 8.9.

Z2:

(A) colloidal silica particles, the total amount of which is 0,01 wt% to 1.8 wt% based on the total weight of the respective CMP composition (B) N-lauroyl sarcosine, the total amount of which is represented by the respective The total weight of the CMP composition is 0,008 wt% to 0,08 wt% (C) at least one amino acid (C) selected from the group consisting of glycine, alanine, leucine, valine, cysteine , serine and proline or their salts, the total amount of which is based on the total weight of the respective CMP composition is 0,35wt% to 0,8wt% (D) hydrogen peroxide, the total amount of which is each The total weight of the CMP composition is 0.2wt% to 1.5wt%, (E) an aqueous medium, wherein the pH of the CMP composition (Q) is 7.8 to 8.9.

Z3:

(A) colloidal silica particles, the total amount of which is 0,01 wt% to 1.8 wt% based on the total weight of the respective CMP composition (B) N-cocoyl sarcosine, the total amount of which is expressed as The total weight of the CMP composition is 0,008 wt% to 0,08 wt% (C) at least one amino acid (C) selected from glycine, alanine, leucine, valine, cysteamine Groups consisting of acids, serine and proline or salts thereof, the total amount of which is 0,35 wt% to 0,8 wt% based on the total weight of the respective CMP composition (D) hydrogen peroxide, the total amount of which is 0,2 wt% to 1.5 wt% based on the total weight of the respective CMP composition, (E) an aqueous medium, wherein the pH of the CMP composition (Q) is 7.8 to 8.9 .

Z4:

(A) colloidal silica particles, the total amount of which is 0,01 wt% to 1.8 wt% based on the total weight of the respective CMP composition (B) 4-dodecylbenzenesulfonic acid, the total amount of which is each The total weight of the CMP composition is 0,008 wt% to 0,08 wt% (C) at least one amino acid (C) selected from glycine, alanine, leucine, valine, cysteamine A group consisting of acid, serine and proline or their salts, the total amount of which is 0,35 wt% to 0,8 wt% based on the total weight of the respective CMP composition (D) hydrogen peroxide, the total amount of which is The total weight of each CMP composition is 0.2wt% to 1.5wt%, (E) an aqueous medium, wherein the pH of the CMP composition (Q) is 7.8 to 8.9.

Z5:

(A) colloidal silica particles, the total amount of which is 0,01 wt% to 1.8 wt% based on the total weight of the respective CMP composition (B) N-cocoyl glutamate, the total amount of which is The total weight of the respective CMP composition is 0,008 wt% to 0,08 wt% (C) at least one amino acid (C) selected from the group consisting of glycine, alanine, leucine, valamine Groups consisting of acids, cysteine, serine and proline or their salts, the total amount of which is 0,35% to 0,8% by weight based on the total weight of the respective CMP composition (D) Hydrogen peroxide , the total amount of which is 0.2 wt% to 1.5 wt% based on the total weight of the respective CMP composition, (E) an aqueous medium, wherein the pH of the CMP composition (Q) is 7.8 to 8.9.

Z6:

(A) colloidal silica particles, the total amount of which is 0,01 wt% to 1.8 wt% based on the total weight of the respective CMP composition (B) monohexyl phosphate, the total amount of which is based on the total weight of the respective CMP composition 0,001% to 0,05% by weight based on the total weight of (C) at least one amino acid (C) selected from the group consisting of glycine, alanine, leucine, valine, cysteine, serine and proline or its salts, the total amount of which is 0,35 wt% to 0,8 wt% (D) hydrogen peroxide, the total amount of which is based on the total weight of the respective CMP composition The total weight is 0.2wt% to 1.5wt%, (E) aqueous medium, wherein the pH of the CMP composition (Q) is 7.8 to 8.9.

Z7:

(A) colloidal silica particles, the total amount of which is 0,01 wt% to 1.8 wt% based on the total weight of the respective CMP composition (B) monooctyl phosphate, the total amount of which is calculated based on the total weight of the respective CMP composition Total weight is 0,001wt% to 0,05% by weight (C) of at least one amino acid (C) selected from the group consisting of glycine, alanine, leucine, valine, cysteine, serine and proline or salts thereof Groups of compositions, the total amount of which is 0,35 wt% to 0,8 wt% based on the total weight of the respective CMP compositions (D) hydrogen peroxide, the total amount of which is 0, based on the total weight of the respective CMP compositions, 2wt% to 1.5wt%, (E) an aqueous medium, wherein the pH of the CMP composition (Q) is 7.8 to 8.9.

Z8:

(A) colloidal silica particles, the total amount of which is 0,01 wt% to 1.8 wt% based on the total weight of the respective CMP composition (B) monodecyl phosphate, the total amount of which is calculated based on the total weight of the respective CMP composition 0,001% to 0,05% by weight based on the total weight of (C) at least one amino acid (C) selected from the group consisting of glycine, alanine, leucine, valine, cysteine, serine and proline or its salts, the total amount of which is 0,35 wt% to 0,8 wt% (D) hydrogen peroxide, the total amount of which is based on the total weight of the respective CMP composition The total weight is 0.2wt% to 1.5wt%, (E) aqueous medium, wherein the pH of the CMP composition (Q) is 7.8 to 8.9.

Z9:

(A) Colloidal silica particles, the total amount of which is 0,01wt% based on the total weight of the respective CMP composition to 1.8% by weight of (B) dihexyl phosphate, the total amount of which is 0,001% to 0,05% by weight, based on the total weight of the respective CMP composition, of (C) at least one amino acid (C) selected from The group consisting of glycine, alanine, leucine, valine, cysteine, serine and proline or their salts, the total amount of which is 0 based on the total weight of the respective CMP composition, 35 wt% to 0,8 wt% (D) hydrogen peroxide, the total amount of which is 0,2 wt% to 1,5 wt% based on the total weight of the respective CMP composition, (E) an aqueous medium, wherein the CMP composition (Q ) has a pH of 7.8 to 8.9.

Z10:

(A) colloidal silica particles, the total amount of which is 0,01 wt% to 1.8 wt% based on the total weight of the respective CMP composition (B) dioctyl phosphate, the total amount of which is calculated based on the total weight of the respective CMP composition 0,001% to 0,05% by weight based on the total weight of (C) at least one amino acid (C) selected from the group consisting of glycine, alanine, leucine, valine, cysteine, serine and proline or its salts, the total amount of which is 0,35 wt% to 0,8 wt% (D) hydrogen peroxide, the total amount of which is based on the total weight of the respective CMP composition The total weight is 0.2wt% to 1.5wt%, (E) aqueous medium, wherein the pH of the CMP composition (Q) is 7.8 to 8.9.

Z11:

(A) Colloidal silica particles, the total amount of which is 0,01 wt% to 1.8 wt% based on the total weight of the respective CMP composition (B) Didecyl phosphate, the total amount of which is based on the total weight of the respective CMP composition 0,001% to 0,05% by weight based on the total weight of (C) at least one amino acid (C) selected from the group consisting of glycine, alanine, leucine, valine, cysteine, serine and proline or its salts, the total amount of which is 0,35 wt% to 0,8 wt% (D) hydrogen peroxide, the total amount of which is based on the total weight of the respective CMP composition The total weight is 0.2wt% to 1.5wt%, (E) aqueous medium, wherein the pH of the CMP composition (Q) is 7.8 to 8.9.

Z12:

(A) colloidal silica particles, the total amount of which is 0,01 wt% to 1.8 wt% based on the total weight of the respective CMP composition (B) mono C ₆ -C ₁₀ phosphate, di C ₆ -C ₁₀ Mixtures of esters, the total amount of which is 0,001 wt% to 0,05 wt% based on the total weight of the respective CMP composition (C) at least one amino acid (C) selected from the group consisting of glycine, alanine, leucine A group consisting of acid, valine, cysteine, serine and proline or their salts, the total amount of which is 0,35 wt% to 0,8 wt% based on the total weight of the respective CMP composition (D ) hydrogen peroxide, the total amount of which is 0,2 wt % to 1.5 wt % based on the total weight of the respective CMP composition, (E) an aqueous medium, wherein the pH of the CMP composition (Q) is 7.8 to 8.9.

Methods of preparing CMP compositions are generally known. These methods can be applied to prepare the CMP compositions used in accordance with the present invention. This can be achieved by dispersing or dissolving components (A), (B), (C), (D) and optional components described above in an aqueous medium (E), preferably water , and optionally by adjusting the pH by adding acids, bases, buffers or pH adjusting agents. For this purpose customary and standard mixing methods and mixing devices such as stirring vessels, high shear impellers, ultrasonic mixers, homogenizer nozzles or countercurrent mixers can be used.

Grinding methods are generally known and can be carried out by these methods and equipment under the conditions customary for CMP in the manufacture of wafers with integrated circuits. There is no limitation on the equipment that can be used to carry out the milling method.

As is known in the art, typical equipment for the CMP process consists of a rotating platen covered with an abrasive pad. Orbital grinders have also been used. Wafers are mounted on carriers or chucks. The processing surface of the wafer faces the polishing pad (single-side polishing method). A retaining ring secures the wafer in a horizontal position.

Below the carrier, the larger diameter platen is also generally positioned horizontally and provides a surface parallel to the surface of the wafer to be ground. The polishing pad on the platen is in contact with the wafer surface during the planarization process.

To generate material loss, the wafer is pressed against a polishing pad. Both the carrier and platen are typically rotated about their respective axes extending perpendicularly from the carrier and platen. The rotating carrier shaft may remain fixed in position relative to the rotating platen, or may oscillate horizontally relative to the platen. The direction of rotation of the carrier is typically (but not necessarily) the same as the direction of rotation of the platen. The rotational speeds of the carrier and platen are generally (but not necessarily) set to different values. During the CMP method of the present invention In between, the CMP composition of the present invention is typically applied to the polishing pad in a continuous flow or in a drop-by-drop manner. Typically, the platen temperature is set at a temperature of 10°C to 70°C.

The load on the wafer can be applied by, for example, a steel plate covered with a soft pad (commonly called a substrate film). In more advanced equipment, a flexible membrane loaded with air or nitrogen pressure is used to press the wafer onto the pad. Such film carriers are better for low downforce methods when using hard pads because the downforce distribution across the wafer is more uniform than that of a carrier with a hard platen design. According to the invention, carriers with the option of controlling the pressure distribution on the wafer can also be used. They are usually designed with a number of different chambers which can be loaded to some extent independently of each other.

For further details, reference is made to WO 2004/063301 A1, in particular page 16, paragraph [0036] to page 18, paragraph [0040] and FIG. 2 .

By means of the CMP method of the invention and/or using the CMP composition of the invention, wafers containing cobalt and/or cobalt alloys with integrated circuits can be obtained which have excellent functionality.

The CMP compositions used according to the invention can be used in the CMP process in the form of ready-to-use slurries which have a long shelf life and which exhibit a stable particle size distribution over a long period of time. Therefore, it is easy to handle and store. It exhibits excellent grinding performance, especially a lower static etch rate of cobalt and/or cobalt alloys and a higher material removal rate (MRR) of cobalt. Since the amounts of its components are kept to a minimum, the CMP compositions used according to the invention can each be used in a cost-effective manner.

Examples and Comparative Examples

The general procedure for CMP experiments is described below.

Standard CMP method for 200mm Co/Co wafer:

Strasbaugh nSpire (model 6EC), ViPRR floating retaining ring carrier; down pressure: 1.5 psi; back side pressure: 1.0 psi; retaining ring pressure: 1.0 psi; grinding table/carrier speed: 130/127 rpm; slurry flow rate: 300 ml /min; grinding time: 15s; (Co) 60s; (Cu) polishing pad: Fujibo H800; substrate film: Strasbaugh, DF200 (136 holes); adjustment tool: Strasbaugh, soft brush, ex-situ; on each wafer Afterwards, the pad was conditioned for subsequent processing of another wafer by 2 sweeps with 5 lbs downward force. The brushes are soft. This means that the brush will not cause a significant removal rate of the soft abrasive pad even after 200 sweeps.

Three dummy TEOS wafers were ground for 60 s, followed by grinding of metal wafers (Co wafers were ground for 15 s).

Agitate the slurry at a local supply station.

Standard analytical procedure for metal blanketed wafers:

The removal rate was measured by the difference in wafer weight before and after CMP, by Sartorius LA310 S scale or NAPSON 4-point probe station.

Radial uniformity of removal rate was evaluated by 39-point diameter scan (scope) using a NAPSON 4-point probe station.

Standard consumables for CMP of metal film coated wafers:

Co membrane: 2000 A PVD Co on Ti bushing (supplier: AMT); pH value was measured with a pH combination electrode (Schott, blue line 22pH electrode).

Standard procedure for measuring Co static etch rate (Co-SER):

Co-SER experiments were performed as follows. 2.5 x 2.5 cm PVD Co (from AMT) was cut and washed with deionized water. Co film thickness (before drying) was measured with a 4-point probe. 400ml of freshly prepared slurry with 0.5% H ₂ O ₂ was placed in a beaker and then brought to 50°C. Place the Co test piece into the slurry and keep it in the slurry for 3 minutes. The coupons were then washed and dried with _N2 . The Co film thickness (after drying) was measured again with the same device. Co-SER was measured by the following formula: SER(A/min)=(before drying-after drying)/3

Standard procedure for slurry preparation:

A 10 wt% glycine aqueous solution was prepared by dissolving the desired amount of glycine in ultrapure water. After stirring for 20 min, the solution was neutralized and the pH adjusted to pH 8.05±0.1 by adding 4.8 wt% aqueous KOH. Balance water can be added to adjust the concentration. By adding the required amount of anionic surfactant Agent (B) was dissolved in ultrapure water and stirred for 30 minutes until all the solids of the anionic surfactant dissolved to prepare 1 wt% stock aqueous solutions of the respective anionic surfactant (B).

To prepare the CMP slurry of the examples, a solution of glycine (amino acid (C)), an anionic surfactant (corrosion inhibitor (B)) was mixed and a solution of colloidal silica particles was added under continuous stirring ( (A), eg 20% stock solution of Fuso ^® PL 3). After the required amount of abrasive (A) has been added, the dispersion is stirred for another 5 minutes. The pH was then adjusted to 8.3±0.1 by adding 4.8 wt% aqueous KOH. Equilibrium water was added under stirring to adjust the concentration of the CMP slurry to the values listed in Table 2 and Table 3 of the Examples and Comparative Examples below. Thereafter, the dispersion was filtered by passing the dispersion through a 0.2 μm filter at room temperature. The required amount of H ₂ O ₂ (D) was added immediately before the slurry was used for CMP (1 to 15 min).

Inorganic particle (A) used in the embodiment

Colloidal cocoon-like silica with an average primary particle size (d1) of 35 nm and an average secondary particle size (d2) of 70 nm (as measured by a Horiba instrument using dynamic light scattering technique) and a specific surface area of about 46 m ² /g was used Particles (A1) (eg Fuso® PL-3).

Procedures for Particle Shape Identification

Disperse the aqueous cocoon-like silica particle dispersion with 20wt% solid content in on carbon foil and dry. Dried dispersions were analyzed by using energy filtration-transmission electron microscopy (EF-TEM) (120 kV) and scanning electron microscopy secondary electron imaging (SEM-SE) (5 kV). EF-TEM images with a resolution of 2k, 16 bit, 0.6851 nm/pixel (Figure 4) were used for this analysis. The image is binary encoded using a threshold after noise suppression. The particles were then separated manually. Overlying and edge particles were identified and were not used for analysis. ECD, shape factor and sphericity as previously defined were calculated and statistically classified.

A2 is the ^agglomerated particle used ( eg Fuso® PL-3H).

The CMP compositions according to the present invention show improved grinding performance in terms of cobalt material removal rate (MRR) [Å/min] and a sharp decrease in Co etch rate, as can be demonstrated by the examples shown in Table 2 and Table 3 .

The diagram shows:

Figure 1: Schematic illustration of shape factor variation with particle shape

Figure 2: Schematic illustration of the variation of sphericity with particle elongation

Figure 3: Schematic illustration of Equivalent Circle Diameter (ECD)

Figure 4: Energy Filtration-Transmission Electron Microscopy (EF-TEM) (120 kV) image of dry cocoon-like silica particle dispersion with 20 wt% solids content on carbon foil

Claims (13)

A use of a chemical mechanical polishing (CMP) composition (Q) for chemical mechanical polishing of a substrate (S) containing (i) cobalt and/or (ii) a cobalt alloy, wherein the CMP composition (Q) contains (A ) Inorganic particles, (B) 0.001wt% to 0.09wt% of the anionic surfactant RS (I) of the general formula (I), wherein R is C ₅ -C ₂₀ alkyl, C ₅ -C ₂₀ alkenyl, C ₅ -C ₂₀ alkyl acyl or C ₅ -C ₂₀ alkenyl acyl and S is a valence group derived from sulfonic acid derivatives, amino acid derivatives or phosphoric acid derivatives or salts or mixtures thereof, (C) at least one amino acid, (D) at least one oxidizing agent, (E) an aqueous medium, and wherein the pH of the CMP composition (Q) is 7-10. Such as the use of the CMP composition (Q) in claim 1, wherein the inorganic particles (A) are colloidal inorganic particles. Such as the use of the CMP composition (Q) in item 2 of the scope of the patent application, wherein the colloidal inorganic particles are silica particles. Such as the use of the CMP composition (Q) in any one of the 1st to 3rd items of the patent scope, wherein the anionic surfactant (B) has the general formula (I) and wherein R is hexyl, heptyl, octyl yl, nonyl, decyl, hexenyl, heptenyl, octenyl, nonyl, decenyl, undecenyl, dodecenyl, oleyl, lauryl or cocoyl and S is derived from sulfonic acid, benzene A valent group of sulfonic acid, monosubstituted benzenesulfonic acid, sarcosine, glutamic acid, phosphoric acid or monophosphate ester or salt thereof. Such as the use of the CMP composition (Q) in any one of the 1st to 3rd items of the patent scope, wherein the anionic surfactant (B) has the general formula (I) and wherein R is hexyl, octyl, deca Monoyl, dodecenyl, oleyl, lauryl or cocoyl and S is derived from sulfonic acid, benzenesulfonic acid, sarcosine, glutamic acid, phosphoric acid or monophosphate or one of their salts price base. Use of the CMP composition (Q) in any one of the first to third items of the patent scope, wherein the at least one amino acid (C) is glycine, alanine, leucine, valine , cysteine, serine and proline or their salts. Such as the use of the CMP composition (Q) in any one of the first to third items of the scope of the patent application, wherein the total amount of the at least one amino acid (C) is based on the total weight of the respective CMP composition 0.1wt% to 2.25wt% range. Use of the CMP composition (Q) according to any one of the claims 1 to 3, wherein the oxidizing agent contains peroxide. As the use of the CMP composition (Q) in any one of the first to third items of the scope of the patent application, wherein the oxidizing agent is hydrogen peroxide. A chemical mechanical polishing (CMP) composition for chemical mechanical polishing substrate (S), which contains: (A) colloidal silica particles, the total amount of which is 0.01wt% based on the total weight of the respective CMP composition to 3 wt%, (B) at least one anionic surfactant (B) selected from N-oleyl sarcosine, N-lauroyl sarcosine, N-cocoyl sarcosine, 4- The group consisting of dodecylbenzenesulfonic acid, N-cocoyl glutamate, and C ₆ -C ₁₀ alkyl phosphate, the total amount of which is 0.001% by weight based on the total weight of the respective CMP composition to 0.09 wt%, (C) at least one amino acid (C) selected from glycine, alanine, leucine, valine, cysteine, serine and proline or salts thereof A group of components, the total amount of which is 0.2 wt% to 0.9 wt% based on the total weight of the respective CMP composition, (D) hydrogen peroxide, the total amount of which is 0.2 wt% based on the total weight of the respective CMP composition wt% to 2wt%, (E) aqueous medium, wherein the pH of the CMP composition (Q) is 7 to 10, wherein the substrate (S) contains (i) cobalt and/or (ii) cobalt alloy, wherein the anion The surfactant (B) alone acts as a corrosion inhibitor for cobalt and/or cobalt alloys without adding other corrosion inhibitors selected from benzotriazole (BTA), derivatives of BTA or triazole. A method of manufacturing a semiconductor device, comprising chemical mechanical polishing of a substrate (S) used in the semiconductor industry in the presence of a CMP composition (Q) as defined in any one of claims 1 to 10, Wherein the substrate (S) contains (i) cobalt and/or (ii) cobalt alloy. Such as the method of claim 11, wherein the static etching rate (SER) of cobalt is less than 100Å/min. The method according to any one of the 11th to 12th claims of the patent application, wherein the cobalt material removal rate (MRR) is adjusted to a range of 300Å/min to 6500Å/min.

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