TW201606066A - A chemical mechanical polishing (CMP) composition - Google Patents

Abstract

A chemical mechanical polishing (CMP) composition (Q) comprising (A) Colloidal or fumed inorganic particles (A) or a mixture thereof in a total amount of from 0.0001 to 2.5 wt.% based on the total weight of the respective CMP composition (B) at least one amino acid in a total amount of from 0,2 to 1 wt.% based on the total weight of the respective CMP composition (C) at least one corrosion inhibitor in a total amount of from 0,001 to 0,02 wt.% based on the total weight of the respective CMP composition (D) hydrogen peroxide as oxidizing agent in a total amount of from 0.0001 to 2 wt.% based on the total amount of the respective CMP composition (E) aqueous medium wherein the CMP composition (Q) has a pH in the range of from 6 to 9.5.

Description

Chemical mechanical polishing composition

The present invention is basically directed to a chemical mechanical polishing (CMP) composition and its use for polishing a substrate comprising cobalt or cobalt and copper and/or cobalt alloys of the semiconductor industry. The CMP composition according to the present invention comprises inorganic particles, at least one amino acid, at least one corrosion inhibitor, hydrogen peroxide, and an aqueous medium. The CMP composition exhibits improved and adjustable polishing performance.

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

CMP is used to planarize the surface of metals and/or oxides during fabrication of materials and devices used in the semiconductor industry. CMP utilizes the interaction of chemical and mechanical interactions to achieve the flatness of the surface to be polished. The chemical action is provided by a chemical composition, also known as a CMP composition or a CMP slurry. Mechanical action is typically performed by a polishing pad, typically pressing the polishing pad against the surface to be abraded and mounting it on a moving platen. The movement of the platen is usually straight, rotating or orbital.

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

With the continuous reduction of feature sizes in ultra-large-scale integrated circuit (ULSI) technology Less, the size of the copper interconnect structure has become smaller and smaller. To reduce the RC delay, the thickness of the barrier or adhesive layer in the copper interconnect structure becomes thinner. The conventional copper barrier/adhesive layer stack Ta/TaN is no longer suitable because the resistivity of Ta is relatively high and copper cannot be directly plated onto Ta. Cobalt has lower resistivity and is less expensive than Ta. The bond between Cu and Co is good. Cu can be easily nucleated on Co, and copper can be directly plated on cobalt.

In an integrated circuit, Co is used as a bonding or barrier layer for copper interconnects, and Co can also be used as a nanocrystal Co in a memory device and as a metal gate in a MOSFET.

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 slurry. In current chemical mechanical polishing processes, most of the current pastes for copper and barrier are acidic in order to reduce damage to low-k dielectrics. However, it has been observed that copper and cobalt are susceptible to being dissolved in an acidic solution containing an oxidizing agent such as hydrogen peroxide. This causes the polishing rate of copper and cobalt to be too high so that it will induce depression of the copper wire. In addition, dissolution of the cobalt adhesion layer on the sidewalls of the copper interconnect structure can cause copper line delamination and cause safety issues.

Depending on the integration scheme used in the ultra-large-scale integrated circuit (ULSI) technology, Co, Cu, and low-k dielectric materials are used in different amounts and thicknesses to coexist selectivity, corrosion, removal rate, and surface quality. The composition of chemical mechanical polishing of semiconductor device fabrication presents a number of challenges.

In the prior art, the use of CMP compositions comprising inorganic particles, at least one amino acid, at least one corrosion inhibitor, hydrogen peroxide and water, and the use of substrates comprising cobalt and/or copper for milling the semiconductor industry are known. And is described, for example, in the following references.

J. Electrochem. Soc. 2012, Vol. 159, No. 6, pp. H582-H588 discloses having 5 wt.% abrasive, 1 wt.% H ₂ O ₂ as oxidizing agent and 0.5 wt.% arginine as a binding agent. The colloidal ceria-based slurry is used for grinding cobalt (Co), and has superior performance at a pH of 10 in terms of surface quality after good grinding and no pit formation. Addition of 5 mM BTA to this slurry inhibited the Cu dissolution rate and produced a Co/Cu removal rate ratio of about 1.2.

The synergistic effect of H ₂ O ₂ and glycine on cobalt CMP in weakly alkaline slurries is disclosed in the microelectronics engineering publication available on February 13, 2014.

US 2013/0140273 A1 discloses a slurry for chemical mechanical polishing of Co. The slurry comprises 0.01% to 2% inhibitor, 0% to 5% oxidizing agent, 0.1% to 10% abrasive, 0.001% to 10%, and water. The pH of the slurry was adjusted to 3-5 by a pH adjuster. The inhibitor is selected from one or more five-membered heterocyclic compounds containing S and N atoms. The oxidizing agent is one or more selected from the group consisting of H ₂ O ₂ , (NH ₄ ) ₂ S ₂ O ₈ , K10 ₄ and KClO ₅ . The abrasive is one or more selected from the group consisting of SiO ₂ , CeO ₂ and Al ₂ O ₃ . The complexing agent is one or more selected from the group consisting of amino acids and citric acid.

Accordingly, there is a great need for readily available CMP compositions and CMP processes that avoid all of the disadvantages associated with prior art, such as low material removal rates of Co, high Cu and/or Co corrosion, and no selective control.

One of the objectives of the present invention is to provide a CMP composition suitable for CMP of substrates comprising cobalt or cobalt and copper and/or cobalt alloys and exhibiting improved polishing performance, particularly between cobalt and copper. . In addition, a CMP composition is sought which inhibits corrosion of cobalt and copper, results in high material removal rates, is compatible with low-k dielectric materials of semiconductor substrates, imparts high quality surface conditioning, reduces dishing, and is neutral to alkaline. Storage in the pH range is stable and will be ready to use. In addition, a corresponding CMP process is provided.

Therefore, a CMP composition was found which contained: (A) colloidal or aerosol-like inorganic particles (A) or a mixture thereof, the total amount of which is 0.0001 wt.% to 2.5 wt.%, based on the total weight of the respective CMP compositions; (B) at least one amino acid, The total amount is 0.2 wt.% to 1 wt.% based on the total weight of the respective CMP compositions; (C) at least one corrosion inhibitor, the total amount of which is 0.001 wt.% based on the total weight of the respective CMP compositions. To 0.02 wt.%; (D) hydrogen peroxide as an oxidizing agent, the total amount of which is 0.0001 wt.% to 2 wt.% based on the total of the respective CMP compositions; (E) water; wherein the CMP composition (Q) The pH of the pH is in the range of 6 to 9.5.

In addition, the above-mentioned objects of the present invention are achieved by a method of fabricating a semiconductor device comprising containing cobalt or cobalt and copper and/or in the presence of the chemical mechanical polishing (CMP) composition (Q). A chemical mechanical polishing is performed on a cobalt alloy or a substrate of a surface region composed of cobalt or cobalt and copper and/or cobalt alloy.

Furthermore, the use of the CMP composition (Q) for chemical mechanical polishing of a substrate (S) used in the semiconductor industry has been found, wherein the substrate (S) comprises (i) cobalt or (ii) cobalt and copper and/or ( Iii) a cobalt alloy to achieve the objectives of the present invention.

Each figure shows:

Figure 1: Schematic illustration of the shape factor as a function of particle shape.

Figure 2: Schematic illustration of the change in sphericity as a function of the elongation of the particles.

Figure 3: Schematic illustration of the equivalent circle diameter (ECD).

Figure 4: Energy filtration-transmission electron microscopy (EF-TEM) (120 kV) image of a dry bismuth dioxide particle dispersion having a solids content of 20 wt.% on a carbon foil.

Figure 5: Cu and Co material removal rates and Co and Cu selectivity versus H ₂ O ₂ concentration at 0.5 wt.% (A) low abrasive concentration.

Figure 6: Correlation of Cu material removal rate with H ₂ O ₂ concentration at a low particle concentration of 0.5 wt.% (A) and a high particle concentration of 4.9 wt.% (A).

Figure 7: Correlation between Co and Cu material removal rates and downward pressure at 1 wt.% H ₂ O ₂ concentration.

Surprisingly, it has been found that the CMP composition (Q) according to the present invention exhibits a very high correlation between the copper material removal rate and the hydrogen peroxide concentration, and gives the opportunity to adjust the cobalt by changing the H ₂ O ₂ concentration. Selectivity with copper. Without being bound by this theory, it is currently believed that this is due to a combination of a low abrasive concentration of less than 2.5 wt.% and a pH in the range of 6 to 9.5.

Preferred specific examples are explained in the scope of the patent application and the specification. It will be understood that combinations of preferred embodiments are within the scope of the invention.

According to the invention, the CMP composition comprises colloidal or aerosolous inorganic particles or a mixture thereof (A).

In general, the colloidal inorganic particles are inorganic particles by the wet precipitation method were; smoke-like inorganic particles by a method using, for example Aerosil ^® high temperature flame hydrolysis with hydrogen chloride, for example, a metal precursor prepared in the presence of oxygen.

(A) can be: - one type of colloidal inorganic particle, - a type of aerosolous inorganic particle, - a mixture of different types of colloidal and/or aerosolous inorganic particles.

According to the invention, the amount of (A) in the CMP composition (Q) is not more than 2.5 wt.%, based on the total weight of the composition (Q). It is preferably not more than 2.0 wt.%, most preferably not more than 1.5 wt.%, especially not more than 0.8 wt.%, based on the total weight of the composition (Q). According to the 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.%, based on the total weight of the composition (Q). Especially at least 0.3 wt.%. For example, the amount of (A) may range from 0.4 wt.% to 1.2 wt.%.

In general, the particles (A) may be contained 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 a multimodal particle size distribution, bimodal is generally preferred. The unimodal particle size distribution of the particles (A) may be preferred in order to have easy reproducibility characteristics and easy reproducibility conditions during the CMP process of the present invention. Generally, the particles (A) preferably have a monomodal particle size distribution.

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

The average particle size of the particles (A) can vary over 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, for example, using dynamic light scattering (DLS) or static light scattering (SLS) methods. These and other methods are well known in the art, see, for example, Kuntzsch, Timo; Witnik, Ulrike; Hollatz, Michael Stintz; Ripperger, Siegfried; Characterization of Slurries Used for Chemical-Mechanical Polishing (CMP) in the Semiconductor Industry; .Eng.Technol; 26 (2003), vol. 12, p. 1235.

For DLS, the Horiba LB-550 V (DLS is typically used, according to the manual Dynamic light scattering measurement) or any other such instrument. This technique measures the hydrodynamic diameter of a particle as it scatters a laser source (λ = 650 nm), which is detected at an angle of 90° or 173° to the incident light. The change in the intensity of the scattered light is due to the random Brownian motion of the particle as it moves through the incident beam and monitors its change 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 a higher velocity and correspond to faster decay.

These decay constants are proportional to the diffusion coefficient D _{t of the} particles and are used to calculate the particle size according to the Stokes-Einstein equation:

It is assumed that the suspended particles (1) have a spherical morphology and (2) are uniformly dispersed (i.e., not aggregated) throughout the aqueous medium (E). This relationship is expected to remain true for particle dispersions containing less than 1 wt.% solids because there is no significant deviation in the viscosity of the aqueous dispersion (E), where n = 0.96 mPa. s (at T = 22 ° C). The particle size distribution of the aerosol or colloidal inorganic particle dispersion (A) is usually measured in a plastic light-melting tank at a solid concentration of 0.1% to 1.0%, and if necessary, diluted with a dispersion medium or ultrapure water.

Preferably, the average particle size of the particles (A) is 20 nm as measured by dynamic light scattering techniques using, for example, a High Performance Particle Sizer (HPPS; from Malvern Instruments, Inc.) or Horiba LB550. It is in the range of 200 nm, more preferably in the range of 25 nm to 180 nm, most preferably in the range of 30 nm to 170 nm, particularly preferably in the range of 40 nm to 160 nm, and especially in the range of 45 nm to 150 nm.

The BET surface of the particles (A) determined according to DIN ISO 9277:2010-09 can vary over a wide range. Preferably, the particles (A) of BET surface 1m ² / g to the inner / g range of 500m ^2, more preferably at 5m ² / g to the inner / g range of 250m ^2, in the best 10m ² / g to 100m ² / g within the range, in particular in the 20m ² / g to 90m ² / g range, for example within 25m ² / g to 85m ² / g range.

The particles (A) may have various shapes. Thus, the particles (A) may have one or substantially only one type of shape. However, it is also possible that the particles (A) have different shapes. For example, there may be two types of particles (A) of different shapes. For example, (A) may have the following shape: cube, cube with hypotenuse, octahedron, icosahedron, scorpion, nodules, and spheres with or without protrusions or dents. Preferably, it is substantially spherical, whereby the particles typically have protrusions or indentations.

It may be preferred that the inorganic particles (A) are in the form of a crucible. The mash may or may not have protrusions or dents. The braided particles are particles having a short axis of 10 nm to 200 nm and a major axis/minor axis ratio of 1.4 to 2.2, more preferably 1.6 to 2.0. The average form factor is preferably from 0.7 to 0.97, more preferably from 0.77 to 0.92, the average sphericity is preferably from 0.4 to 0.9, more preferably from 0.5 to 0.7, and the average equivalent circle diameter is preferably from 41 nm to 66 nm, more preferably from 48 nm to 60 nm, which can be determined by transmission electron microscopy and scanning electron microscopy.

The determination of the form factor, sphericity, and equivalent circle diameter of the braided particles is described below with reference to FIGS. 1 through 4.

The form factor gives information about the shape and dent of individual particles (see Figure 1) and can be calculated according to the following formula: Form factor = 4 π (area / perimeter ² )

The shape factor of the dent-free spherical particles is 1. The value of the form factor decreases as the number of dimples increases.

The sphericity (see Figure 2) gives information about the elongation of individual particles using moments of the mean and can be calculated according to the following equation, where M is the center of gravity of the individual particles: 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/spherical) ^0.5

Where Mxx=Σ(xx _average ) ² /N

Myy=Σ(yy _average ) ² /N

Mxy=Σ[(xx _average )*(yy _average )/N

N The number of pixels that form the image of each particle

The coordinates of x, y pixels

The _{average value of} x forms the average of the x-coordinates of the N pixels of the image of the particles

y _average forms the average of the y coordinates of the N pixels of the image of the particles

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

The equivalent circle diameter of individual non-circular particles (hereinafter also abbreviated as ECD) gives information on the diameter of a circle having the same area as the respective non-circular particles (see Fig. 3).

The average form factor, average sphericity, and average ECD are the arithmetic mean of the individual characteristics associated with the number of particles analyzed.

The procedure for characterizing particle shapes is as follows. An aqueous crucible ceria particle dispersion having a solids content of 20 wt.% was dispersed on a carbon foil and dried. The dried dispersion was analyzed by energy filtration-transmission electron microscopy (EF-TEM) (120 kV) and scanning electron microscopy secondary electron image (SEM-SE) (5 kV). An EF-TEM image (see Figure 4) with a resolution of 2k, 16 bits, 0.6851 nm/pixel was used for this analysis. Use threshold to image after noise suppression Perform binary encoding. Then manually separate the particles. Overlying particles and edge particles are discerned and are not used for this analysis. The ECD, form factor, and sphericity as previously defined are calculated and statistically classified.

For example, the braided particles may be FUSO ^® PL-3 manufactured by Fuso Chemical Co., Ltd. having an average primary particle size (d1) of 35 nm and an average secondary particle size (d2) of 70 nm.

The chemical nature of the particles (A) is not particularly limited. (A) A mixture of particles which may have the same chemical properties or are of different chemical nature. Generally, particles (A) having the same chemical properties are preferred.

In general, (A) may be: - inorganic particles such as metals, metal oxides or carbides, including metalloids, metalloid oxides or carbides, or - mixtures of inorganic particles.

More preferably, the particles (A) are colloidal or aerosol-like inorganic particles or a mixture thereof. Among them, oxides and carbides of metals or metalloids are preferred. More preferably, the particles (A) are alumina, ceria, copper oxide, iron oxide, nickel oxide, manganese oxide, cerium oxide, cerium nitride, cerium carbide, tin oxide, titanium oxide, titanium carbide, tungsten oxide, Cerium oxide, zirconium oxide or a mixture or composite thereof. Most preferably, the particles (A) are alumina, ceria, ceria, titania, zirconia or mixtures or composites thereof. Specifically, the particles (A) are cerium oxide. For example, the particles (A) are colloidal cerium oxide.

As used herein, the term "colloidal cerium oxide" refers to cerium oxide which has been prepared by polycondensation of Si(OH) ₄ . The precursor Si(OH) ₄ can be obtained, for example, by hydrolyzing a high purity alkoxysilane or by acidifying an aqueous citrate solution. Such colloidal silicon dioxide can be prepared according to U.S. Patent No. 5,230,833 or any of various commercially available products, such as ^{Fuso ® PL-1, PL-} 2, PL-3, and products, and Nalco ^® 1050,2327 and 2329 products, and other similar products available from DuPont, Bayer, Applied Research, Nissan Chemical or Clariant.

According to the invention, the CMP composition comprises at least one amino acid (B).

In general, an organic compound having an amine group and an acid group is referred to as an amino acid. For the purposes of the present invention, all individual stereoisomers and their racemic mixtures are also considered to be amino acids. Preferably, both the amine group and the acid group are attached to the same carbon (referred to as an alpha-amino carboxylic acid) for use as a chemical additive in the CMP slurry. Many alpha-amino carboxylic acids are known and there are twenty "natural" amino acids present as essential components of proteins in living organisms. The amino acid may be hydrophilic, neutral or hydrophobic depending on its side chain in the presence of an aqueous carrier. The addition of alpha amino acid as a grinding additive increases the metal removal rate.

At least one α-amino acid (B) can be represented by the formula (I): H ₂ N-CR ¹ R ² COOH (I)

Wherein R ¹ and R ² are independently of each other hydrogen; a cyclic, branched, and straight-chain moiety having 1 to 8 carbon atoms which is unsubstituted or substituted with one or more substituents selected from the group consisting of nitrogen-containing substitutions The base, 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, the at least one amino acid (B) is α-alanine, arginine, aspartic acid, cystine, cysteine, glutamic acid, glutamic acid, glycine, group Aminic acid, isoleucine, leucine, lysine, methionine, phenylalanine, valine, serine, threonine, tryptophan, tyrosine, valine and mixtures thereof And salt. More preferably, (B) is α-alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, leucine, lysine, lysine, serine, Proline and its mixtures and salts. Most preferably, (B) is alpha-alanine, aspartic acid, Glutenin, glycine, valine, serine, and mixtures and salts thereof, specifically (B) are alpha-alanine, aspartic acid, glycine, and mixtures and salts thereof, for example (B) ) is glycine.

According to the invention, the amount of the amino acid (B) in the CMP composition (Q) is not more than 1 wt.%, based on the total weight of the composition (Q). More preferably, it is not more than 0.9 wt.%, most preferably not more than 0.85 wt.%, especially not more than 0.8 wt.%, based on the total weight of the composition (Q). According to the invention, the amount of (B) is at least 0.2 wt.%, 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.%, based on the total weight of the composition (Q). For example, the amount of (B) may range from 0.65 wt.% to 0.78 wt.%.

According to the invention, the CMP composition (Q) comprises at least one corrosion inhibitor. For example, two corrosion inhibitors can be included in the CMP composition (Q).

In general, a corrosion inhibitor is a compound that protects the surface of a metal (e.g., copper) by forming a protective molecular layer on the surface of the metal.

The corrosion inhibitor (C) can be, for example, a diazole, a triazole, a tetrazole or a derivative thereof. Preferably, the at least one corrosion inhibitor (C) may be, for example, 1,2,4 triazole, 1,2,3 triazole, 3-amino-methyl-1H-1,2,4-triazole, Benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, 5-6-dimethylbenzotriazole, 5-chlorobenzotriazole, 1-octylbenzotriene Oxazole, carboxy-benzotriazole, butyl-benzotriazole, 6-ethyl-1H-1,2,4 benzotriazole, (1-pyrrolidinylmethyl)benzotriazole, 1- n-Butyl-benzotriazole, benzotriazole-5-carboxylic acid, 4,5,6,7-tetrahydro-1H-benzotriazole, imidazole, benzimidazole and derivatives thereof and mixtures thereof; Preferably, the at least one corrosion inhibitor (C) can be, for example, 1,2,4 triazole, 1,2,3 triazole, benzotriazole, 4-methylbenzotriazole, 5-methylbenzo Triazole, 5-6-dimethylbenzotriazole, 5-chlorobenzotriazole, 1-n-butyl-benzotriazole, benzotriazole-5-carboxylic acid, 4,5,6,7 - tetrahydro-1H-benzotriazole, imidazole, benzimidazole and derivatives thereof and mixtures thereof; optimally, at least A corrosion inhibitor (C) can be, for example, 1,2,4 triazole, benzotriazole, 5-methylbenzotriazole, 5-chlorobenzotriazole, benzotriazole-5-carboxylic acid, 4 , 5,6,7-tetrahydro-1H-benzotriazole, imidazole and derivatives thereof and mixtures thereof; in particular, at least one corrosion inhibitor (C) may be, for example, 1,2,4 triazole, benzene And triazole, 5-methylbenzotriazole, 5-chlorobenzotriazole, imidazole and derivatives thereof, and mixtures thereof, such as 1H-benzotriazole.

According to the invention, the amount of (C) in the CMP composition (Q) is not more than 0.02 wt.%, based on the total weight of the composition (Q). It is preferably not more than 0.018 wt.%, most preferably not more than 0.016 wt.%, especially not more than 0.014 wt.%, based on the total weight of the composition (Q). According to the invention, the amount of (C) is at least 0.001 wt.%, preferably at least 0.002 wt.%, more preferably at least 0.005 wt.%, most preferably at least 0.007 wt.%, based on the total weight of the composition (Q). In particular at least 0.008 wt.%. For example, the amount of (C) may range from 0.009 wt.% to 0.012 wt.%.

According to the invention, the CMP composition (Q) comprises hydrogen peroxide (D) as an oxidizing agent.

In general, the oxidizing agent is a compound capable of oxidizing one of the layers of the substrate to be polished or the substrate to be polished.

According to the present invention, the amount of (D) in the CMP composition (Q) is not more than 2 wt.%, preferably not more than 1.5 wt.%, more preferably not more than 1.4 wt.%, based on the total weight of the composition (Q). It is preferably not more than 1.3 wt.%, especially not more than 1.2 wt.%. According to the invention, the amount of (D) is at least 0.0001 wt.%, preferably at least 0.03 wt.%, more preferably at least 0.08 wt.%, most preferably at least 0.1 wt.%, based on the total weight of the composition (Q). Especially at least 0.2 wt.%. For example, the amount of (D) may be from 0.02 wt.% to 0.1 wt.%, from 0.15 wt.% to 0.8 wt.%, from 0.8 wt.% to 1.9 wt.%, based on the total weight of the composition (Q). Within the scope.

According to the invention, the CMP composition comprises an aqueous medium (E). (E) may be a type of aqueous medium or a mixture of different types of aqueous medium.

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

If the amount of the 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 stability, polishing efficiency and etching behavior of the CMP composition according to the present invention, respectively, such as the composition compared to different materials (e.g., metal versus cerium oxide) may depend on the pH of the corresponding composition.

According to the invention, the pH of the CMP composition (Q) is in the range of 6 to 9.5. Preferably, the pH of the composition used or according to the invention is in the range of 6.8 to 9.2, more preferably 7 to 8.8, most preferably 7.3 to 8.7, particularly preferably 7.5 to 8.5 (e.g., 7.6 to 8.4).

The CMP composition (Q) of the present invention may further optionally contain at least one nonionic surfactant (F).

In general, the surfactant used in the CMP composition is an interfacial active compound that lowers the surface tension of the liquid, the interfacial tension between the two liquids, or the interfacial tension between the liquid and the solid.

In general, any nonionic surfactant (F) can be used.

The nonionic surfactant (F) is preferably water-soluble and/or water-dispersible, more preferably water-soluble. "Water-soluble" means at the molecular level, the composition of the present invention The relevant components or ingredients of the substance can be dissolved in the aqueous phase. "Water-dispersible" means that the relevant component or component of the composition of the invention can be dispersed in the aqueous phase and form a stable emulsion or suspension.

The nonionic surfactant (F) is preferably an amphiphilic nonionic surfactant, that is, a surfactant comprising at least one hydrophobic group (b1) and at least one hydrophilic group (b2). This means that the nonionic surfactant (F) may comprise more than one hydrophobic group (b1), for example 2, 3 or more than 3 groups (b1), which are at least one hydrophilic as described below The groups (b2) are separated from each other. This also means that the nonionic surfactant (F) may comprise more than one hydrophilic group (b2), for example 2, 3 or more than 3 groups (b2), which are hydrophobic as described below. The groups (b1) are separated from each other.

Thus, the nonionic surfactant (F) can have a different general block structure. Examples of such general block-like structures are: - b1-b2, - b1-b2-b1, - b2-b1-b2, - b2-b1-b2-b1, - b1-b2-b1-b2-b1, And - b2-b1-b2-b1-b2.

The nonionic surfactant (F) is more preferably a two-energetic nonionic surfactant comprising a polyoxyalkylene group.

The hydrophobic group (b1) is preferably an alkyl group, more preferably 4 to 40, most preferably 5 to 20, particularly preferably 7 to 18, specifically 10 to 16 (for example, 11 to 14) ) An alkyl group of carbon atoms.

The hydrophilic group (b2) is preferably a polyoxyalkylene group. The polyoxyalkylene groups can be oligomeric or polymeric. More preferably, the hydrophilic group (b2) is a hydrophilic group selected from the group consisting of polyoxyalkylene groups: (b21) an oxygen-extended alkyl monomer unit, and (b22) an oxygen-removing alkyl group An oxygen-extended alkyl monomer unit other than the monomer unit, the monomer unit (b21) is not the same as the monomer unit (b22), and the (b2) polyoxyalkylene group is randomly, alternately, and has a gradient / or block-like distribution of monomer units (b21) and (b22).

Most preferably, the hydrophilic group (b2) is a hydrophilic group selected from the group consisting of polyoxyalkylene groups: (b21) an oxygen-extended ethyl monomer unit, and (b22) an oxygen-removing ethyl group The oxygen-extended alkyl monomer unit other than the monomer unit, the (b2) polyoxyalkylene group having monomer units (b21) and (b22) distributed in random, alternating, gradient and/or block form.

Preferably, the oxygen-extended alkyl monomer unit (b22) other than the oxygen-extended ethyl monomer unit is a substituted oxygen-extended alkyl monomer unit, wherein the substituent is selected from the group consisting of alkyl groups, rings Alkyl, aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl. The oxygen-extended alkyl monomer unit (b22) other than the oxygen-extended ethyl monomer unit: - more preferably derived from a substituted ethylene oxide (X) wherein the substituent is selected from the group consisting of alkyl groups, Cycloalkyl, aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl, - preferably derived from alkyl substituted epoxy Alkane (X), Particularly preferably derived from substituted ethylene oxide (X) wherein the substituent is selected from the group consisting of alkyl groups having from 1 to 10 carbon atoms, for example derived from methyl oxirane (propylene oxide) And / or ethyl oxirane (butylene oxide).

The substituent of the substituted ethylene oxide (X) may itself carry an inert substituent, that is, it does not adversely affect the interfacial activity of the ethylene oxide (X) and the nonionic surfactant (F). Polymerized substituents. Examples of such inert substituents are a fluorine atom and a chlorine atom, a nitro group and a nitrile group. If such an inert substituent is present, it is used in such an amount that it does not adversely affect the hydrophilic-hydrophobic balance of the nonionic surfactant (F). Preferably, the substituent of the substituted ethylene oxide (X) does not carry such an inert substituent.

The substituent of the substituted ethylene oxide (X) is preferably selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a spiro ring, an outer ring and/or an annealed configuration having 5 to 10 a cycloalkyl group of carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl-cycloalkyl group having 6 to 20 carbon atoms, an alkyl-aryl group having 7 to 20 carbon atoms, 11 to a cycloalkyl-aryl group of 20 carbon atoms and an alkyl-cycloalkyl-aryl group having 12 to 30 carbon atoms. Most preferably, the substituent of the substituted ethylene oxide (X) is selected from the group consisting of alkyl groups having 1 to 10 carbon atoms. Specifically, the substituent of the substituted ethylene oxide (X) is selected from the group consisting of alkyl groups having 1 to 6 carbon atoms.

Examples of the most preferred substituted ethylene oxide (X) are methyloxirane (propylene oxide) and/or ethyloxirane (butylene oxide), especially methyloxirane.

Most preferably, the hydrophilic group (b2) consists of monomer units (b21) and (b22).

In another embodiment, the hydrophilic group (b2) is preferably a polyoxyethylene group, a polyoxyalkylene group or a polyoxybutylene group, more preferably a polyoxyalkylene group.

In the case where the hydrophilic group (b2) comprises or consists of the monomer units (b21) and (b22), the polyoxyalkylene group serving as the hydrophilic group (b2) contains random, alternating, gradient and/or Block-like distribution of monomer units (b21) and (b22). This means that a hydrophilic group (b2) can have only one type of distribution, that is, - random: ...-b21-b21-b22-b21-b22-b22-b22-b21-b22-... ;- Alternate: ...-b21-b22-b21-b22-b21-...;- Gradient: ...b21-b21-b21-b22-b21-b21-b22-b22-b21-b22-b22- B22-...; or - block shape: ...-b21-b21-b21-b21-b22-b22-b22-b22-....

Alternatively, the hydrophilic group (b2) may also contain at least two types of distribution, such as oligomeric or polymeric fragments having a random distribution and oligomeric or polymeric fragments having alternating distribution. Most preferably, the hydrophilic group (b2) preferably has a distribution of only one type, and optimally, the distribution is random or block-like.

In the specific example in which the hydrophilic group (b2) comprises or consists of the monomer units (b21) and (b22), the molar ratios of (b21) and (b22) can be widely varied, and thus can be most advantageously adjusted To meet the specific requirements of the compositions, methods, and uses of the present invention. Mohr ratio (b21): (b22) is preferably from 100:1 to 1:1, more preferably from 60:1 to 1.5:1 and most preferably from 50:1 to 1.5:1, and particularly preferably from 25:1 to 1.5:1, and especially 15:1 to 2:1, and for example 9:1 to 2:1.

Further, the degree of polymerization of the oligomeric and polymeric polyoxyalkylene groups serving as the hydrophilic group (b2) can vary widely, and thus can be most advantageously adjusted to suit the specific requirements of the compositions, methods, and uses of the present invention. Preferably, the degree of polymerization is from 5 to 100, preferably from 5 to 90 and most preferably from 5 to Within the scope of 80.

In particular, the nonionic surfactant (F) is an amphiphilic nonionic polyoxyethylidene-polyoxypropylpropyl ether surfactant which contains an average of 10 to 16 carbon atoms. a mixture of molecules having 5 to 20 oxygen-extended ethyl monomer units (b21) and 2 to 8 oxygen-extended propyl monomer units. For example, the nonionic surfactant (F) is an amphiphilic nonionic polyoxyethylidene-polyoxypropyl propyl alkyl ether surfactant which has an average of from 11 to 14 carbon atoms. And a mixture of molecules having a random distribution of 12 to 20 oxygen-extended ethyl monomer units and 3 to 5 oxygen-extended propyl monomer units.

If present, the nonionic surfactant (F) can be included in the CMP composition (Q) in varying amounts. Preferably, the amount of (F) is not more than 10 wt.%, more preferably not more than 3 wt.%, most preferably not more than 1 wt.%, particularly preferably not more than 0.5 wt.%, based on the total weight of the composition (Q). In particular, it is not more than 0.1 wt.%, for example not more than 0.05 wt.%. Preferably, the amount of (F) is at least 0.00001 wt.%, more preferably at least 0.0001 wt.%, most preferably at least 0.0008 wt.%, particularly preferably at least 0.002 wt.%, based on the total weight of the composition (Q). In particular at least 0.005 wt.%, for example at least 0.008 wt.%.

In general, the nonionic surfactant (F) can have different weight average molecular weights. The weight average molecular weight of (F) is preferably at least 300, more preferably at least 500, most preferably at least 700, especially at least 800, such as at least 900. The weight average molecular weight of (F) is preferably not more than 15,000 [g/mol], more preferably not more than 6,000 [g/mol], as determined by gel permeation chromatography (hereinafter abbreviated as "GPC"). It is not more than 3,000 [g/mol], especially not more than 2,000 [g/mol], for example, not more than 1,400 [g/mol]. Specifically, the weight average molecular weight of (F) is from 900 [g/mol] to 1,400 [g/mol] as determined by GPC. These GPCs are standard GPC techniques known to those skilled in the art.

In general, the solubility of nonionic surfactant (F) in aqueous media Can vary within a wide range. The solubility in (F) in water (pH 7) at 25 ° C is preferably at least 1 g/L, more preferably at least 5 g/L, most preferably at least 20 g/L, in particular at least 50 g/ L, for example at least 150 g/L. The solubility can be determined by evaporating the solvent and measuring the residual mass in the saturated solution.

The CMP composition of the present invention may further optionally contain at least one additional complexing agent (G) different from at least one amino acid (B), such as a complexing agent. In general, the complexing agent is a compound capable of aligning ions of one of the layers of the substrate to be polished or the substrate to be polished. Preferably, (G) is a carboxylic acid having at least one COOH group, an N-containing carboxylic acid, an N-containing sulfonic acid, an N-containing sulfuric acid, an N-containing phosphonic acid, an N-containing phosphoric acid or a salt thereof. More preferably, (G) is a carboxylic acid having at least two COOH groups, an N-containing carboxylic acid or a salt thereof. For example, the at least one additional complexing agent (G) may be acetic acid, gluconic acid, lactic acid, nitrogen-based acetic acid, ethylenediaminetetraacetic acid (EDTA), imido-d-succinic acid, glutaric acid, citric acid , malonic acid, 1,2,3,4-butane tetracarboxylic acid, fumaric acid, tartaric acid, succinic acid and phytic acid.

If present, the complexing agent (G) may be contained in varying amounts. Preferably, the amount of (G) is not more than 20 wt.%, more preferably not more than 10 wt.%, most preferably not more than 5 wt.%, such as not more than 2 wt.%, based on the total weight of the respective 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.%, such as at least 1 wt.%, based on the total weight of the respective composition.

The CMP composition of the present invention may further optionally contain at least one biocide (H), such as a biocide. In general, biocides are compounds that prevent, render harmless or exert a controlling effect on any harmful organism by chemical or biological means. Preferably, (H) is a quaternary ammonium compound, an isothiazolinone-based compound, an N-substituted diazide dioxide or an N'-hydroxy-diazoene oxide salt. More preferably, (H) is an N-substituted diazide dioxide Or N'-hydroxy-diazoene oxide salt.

If present, the biocide (H) can be included in varying amounts. If present, the amount of (H) is preferably not more than 0.5 wt.%, more preferably not more than 0.1 wt.%, most preferably not more than 0.05 wt.%, especially not more than 0.02 wt.%, based on the total weight of the corresponding composition. For example, it is 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 at least 0.006, based on the total weight of the respective composition. Wt.%.

The CMP composition according to the present invention may also contain, if desired, various other additives, including but not limited to pH adjusters, stabilizers, and the like. Such other additives are, for example, additives commonly used in CMP compositions and are therefore known to those skilled in the art. This addition may, for example, stabilize the dispersion or improve the milling performance or selectivity between the different layers.

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

The semiconductor device can be fabricated by a method of performing CMP of a substrate in the presence of the CMP composition of the present invention. According to the invention, the method comprises CMPing a substrate comprising a surface region comprising cobalt or cobalt and copper and/or cobalt alloy or consisting of cobalt or cobalt and copper and/or cobalt alloy.

In general, a semiconductor device which can be manufactured by the method according to the present invention is not particularly limited. Thus, the semiconductor device can be an electronic component comprising a semiconductor material such as, for example, tantalum, niobium and III-V materials. Semiconductor devices can be manufactured or fabricated as a single discrete device It is a device of an integrated circuit (IC) composed of a plurality of devices fabricated and interconnected on a wafer. The semiconductor device can be a two-terminal device (eg, a diode), a three-terminal device (eg, 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 can be a logic device such as an integrated circuit and a microprocessor or a memory device such as a random access memory (RAM), a read only memory (ROM), and a phase change random access memory (PCRAM). Preferably, the semiconductor device is a multi-terminal logic device. In particular, the semiconductor device is an integrated circuit or a microprocessor.

In general, in an integrated circuit, Co is used as a bonding or barrier layer for copper interconnects. In its nanocrystalline form, Co is contained, for example, in a memory device and acts as a metal gate in a MOSFET. Cobalt can also be used as a seed crystal to effect copper plating by electrodeposition. Cobalt or cobalt alloys can also be used in place of copper for one or more layers of wiring. For example, a capacitor (CAP) can be formed in a continuous layer of the same level by metal, insulator, metal (MIM), and thin film resistors. Circuit designers can now wire to the lowest metal level TaN thin film resistors, reducing parasitics and allowing for more efficient use of existing wiring levels. Excess copper and/or cobalt and a cohesive/barrier layer (such as Co/TaN, Co/TiN, Co/TaCN, Co/TiCN) containing Co in the form of, for example, metal nitride or metal carbonitride, or above, for example, a dielectric The single cobalt alloy layer (such as CoMo, CoTa, CoTi, and CoW) can be removed by the CMP process according to the present invention.

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

In general, the cobalt and/or cobalt alloy can be of any type, form or shape. The cobalt and/or cobalt alloy preferably has a layer and/or an overgrown shape. If the cobalt and/or cobalt alloy has a layer and/or an overgrown shape, the cobalt and/or cobalt alloy content is preferably greater than 90%, more preferably greater than 95%, by weight of the corresponding layer and/or overgrowth. Preferably it is greater than 98%, especially greater than 99%, such as greater than 99.9%. The cobalt and/or cobalt alloy has preferably been filled or grown in trenches or plugs between other substrates, more preferably in dielectric materials (eg, SiO ₂ , germanium, low k (BD1, BD2) or ultra low k Filling or growing in trenches or plugs in materials and other separation and semiconductor materials used in the semiconductor industry.

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

According to the method of the present invention, the downward pressure is 2 psi or less. Preferably, the downward pressure is in the range of 0.1 psi to 1.9 psi, more preferably in the range of 0.3 psi to 1.8 psi, most preferably in the range of 0.4 psi to 1.7 psi, and particularly preferably in the range of 0.8 psi to 1.6 psi. For example 1.3 psi.

If the method of the present invention comprises chemical mechanical polishing of a substrate comprising a surface region comprising cobalt and copper or consisting of cobalt and copper, the selectivity of cobalt to copper for material removal rate is preferably greater than 0.05, more preferably greater than 0.2. Preferably, it is above 1, especially above 2.5, especially above 20, for example above 40. This selective feature can be adjusted, for example, by varying the concentration of hydrogen peroxide (D), the concentration of corrosion inhibitor (C), and the concentration of abrasive (A) of the CMP composition (Q).

The CMP composition (Q) used in accordance with the present invention is used in chemical mechanical polishing of substrates comprising cobalt or cobalt and copper and/or cobalt alloys used in the semiconductor industry.

The cobalt and/or cobalt alloy can be of any type, form or shape. The cobalt and/or cobalt alloy preferably has a layer and/or an overgrown shape. If the cobalt and/or cobalt alloy has a layer and/or an overgrown shape, the cobalt and/or cobalt alloy content is preferably greater than 90%, more preferably greater than 95%, by weight of the corresponding layer and/or overgrowth. Preferably it is 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 (eg, SiO ₂ , germanium, low k (BD1, BD2) or ultra low k Filling or growing in trenches or plugs in materials and other separation and semiconductor materials used in the semiconductor industry. For example, in the intermediate process of the Through Silicon Vias (TSV), after the TSV is displayed from the back side of the wafer, in terms of insulation/separation characteristics, such as a polymer, a photoresist, and/or a polyimide. The separation material can be used as an insulating material between subsequent processing steps of wet etching and CMP. A thin layer of barrier material may be present between the included copper and dielectric material. In general, the barrier material that prevents diffusion of metal ions into the dielectric material can be, for example, Ti/TiN, Ta/TaN or Ru or a Ru alloy, Co or Co alloy. If the CMP composition (Q) according to the present invention is used for grinding a substrate comprising cobalt and copper, the selectivity of cobalt to copper with respect to material removal rate is preferably higher than 0.05, more preferably higher than 0.2, and most preferably higher than 1 , in particular above 2.5, in particular above 20, for example above 40. Selectivity can advantageously be adjusted by a combination of high material removal rate (MRR) of cobalt and low MRR of copper (or vice versa).

Example of CMP composition (Q) according to the present invention

Z1: (A) colloidal or aerosol-like inorganic particles (A) or a mixture thereof, the total amount of which is 0.05 wt.% to 0.9 wt.%, based on the total weight of the respective CMP compositions; (B) at least one amine group The total amount of the acid is from 0.2 wt.% to 0.9 wt.% based on the total weight of the respective CMP compositions; (C) at least one corrosion inhibitor, the total amount of which is based on the total weight of the respective CMP compositions 0.008 wt.% to 0.02 wt.%; (D) hydrogen peroxide as an oxidizing agent, the total amount of which is 0.0001 wt.% to 0.1 wt.%, based on the total of the respective CMP compositions; (E) an aqueous medium; The pH of the CMP composition (Q) is in the range of 7.1 to 9.

Z2: (A) colloidal inorganic particles (A), the total amount of which is 0.0001 wt.% to 2.5 wt.%, based on the total weight of the respective CMP compositions; (B) at least one amino acid, the total amount of which is The total weight of the respective CMP compositions is from 0.2 wt.% to 1 wt.%; (C) at least one corrosion inhibitor, the total amount of which is from 0.001 wt.% to 0.02 wt% based on the total weight of the respective CMP compositions. (D) Hydrogen peroxide as an oxidizing agent, the total amount of which is 0.0001 wt.% to 2 wt.% based on the total of the respective CMP compositions; (E) an aqueous medium; wherein the pH of the CMP composition (Q) In the range of 6 to 9.5.

Z3: (A) aerosol-like inorganic particles (A), the total amount of which is 0.0001 wt.% to 2.5 wt.%, based on the total weight of the respective CMP compositions; (B) at least one amino acid, the total amount of which is The total weight of the respective CMP compositions is from 0.2 wt.% to 1 wt.%; (C) at least one corrosion inhibitor, the total amount of which is based on the total weight of the respective CMP compositions. 0.001 wt.% to 0.02 wt.%; (D) hydrogen peroxide as an oxidizing agent, the total amount of which is 0.0001 wt.% to 2 wt.% based on the total of the respective CMP compositions; (E) an aqueous medium; The pH of the CMP composition (Q) is in the range of 6 to 9.5.

Z4: (A) colloidal cerium oxide particles (A), the total amount of which is 0.0001 wt.% to 2.5 wt.%, based on the total weight of the respective CMP compositions; (B) at least one amino acid, the total of which The amount is from 0.2 wt.% to 1 wt.%, based on the total weight of the respective CMP compositions; (C) at least one corrosion inhibitor, the total amount of which is from 0.001 wt.% to 0.02 based on the total weight of the respective CMP compositions. Wt.%; (D) hydrogen peroxide as an oxidizing agent, the total amount of which is 0.0001 wt.% to 2 wt.% based on the total of the respective CMP compositions; (E) an aqueous medium; wherein the CMP composition (Q) The pH is in the range of 6 to 9.5.

Z5: (A) colloidal cerium oxide particles (A), the total amount of which is 0.0001 wt.% to 2.5 wt.%, based on the total weight of the respective CMP compositions, wherein the average particle size of the particles (A) is dynamic light The scattering technique is determined to be 20 nm to 200 nm; (B) at least one amino acid, the total amount of which is 0.2 wt.% to 1 wt.%, based on the total weight of the respective CMP compositions; (C) at least one corrosion inhibitor, the total amount of which is 0.001 wt.% to 0.02 wt.% based on the total weight of the respective CMP compositions; (D) hydrogen peroxide as an oxidizing agent, the total amount of which is composed of individual CMP The total amount of the substance is from 0.0001 wt.% to 2 wt.%; (E) an aqueous medium; wherein the pH of the CMP composition (Q) is in the range of from 6 to 9.

Z6: (A) colloidal cerium oxide particles (A), the total amount of which is 0.0001 wt.% to 2.5 wt.%, based on the total weight of the respective CMP compositions; (B) is glycine, alanine, A total amount of leucine, cysteine or a mixture or salt thereof, from 0.45 wt.% to 0.82 wt.%, based on the total weight of the respective CMP compositions; (C) at least one corrosion inhibitor, the total amount thereof 0.001 wt.% to 0.02 wt.%, based on the total weight of the respective CMP compositions; (D) hydrogen peroxide as the oxidizing agent, the total amount of which is 0.0001 wt.% to 2 wt based on the total of the respective CMP compositions. (E) an aqueous medium; wherein the pH of the CMP composition (Q) is in the range of 6 to 9.5.

Z7: (A) colloidal cerium oxide particles (A), the total amount of which is 0.1 wt.% to 1.8 wt.%, based on the total weight of the respective CMP compositions; (B) is glycine, alanine, a total amount of leucine, cysteine or a mixture or salt thereof, from 0.2 wt.% to 0.9 wt.%, based on the total weight of the respective CMP compositions; (C) at least one corrosion inhibitor, the total amount of which is 0.007 wt.% to 0.018 wt.%, based on the total weight of the respective CMP compositions; (D) hydrogen peroxide as the oxidant, the total amount of which is composed of the respective CMP The total amount of the substance is from 0.0001 wt.% to 2 wt.%; (E) an aqueous medium; wherein the pH of the CMP composition (Q) is in the range of from 6 to 9.5.

Z8: (A) colloidal cerium oxide particles (A), the total amount of which is 0.1 wt.% to 1.8 wt.%, based on the total weight of the respective CMP compositions; (B) is glycine, alanine, The total amount of leucine and cysteine is 0.2 wt.% to 0.9 wt.% based on the total weight of the respective CMP compositions; (C) is 5 methyl-benzotriazole, 1,2, 4 triazole, 1H-benzotriazole, benzotriazole or a mixture thereof, the total amount of which is 0.007 wt.% to 0.018 wt.% based on the total weight of the respective CMP composition; (D) hydrogen peroxide as The oxidizing agent, the total amount of which is 0.0001 wt.% to 2 wt.% based on the total of the respective CMP compositions; (E) an aqueous medium; wherein the pH of the CMP composition (Q) is in the range of 6 to 9.5.

Z9: (A) colloidal or aerosol-like inorganic particles (A) or a mixture thereof, the total amount of which is 0.05 wt.% to 0.9 wt.%, based on the total weight of the respective CMP compositions; (B) at least one amine group The total amount of the acid is from 0.2 wt.% to 0.9 wt.%, based on the total weight of the respective CMP compositions; (C) at least one corrosion inhibitor, the total amount of which is from 0.008% by weight to 0.02% by weight based on the total weight of the respective CMP compositions; (D) hydrogen peroxide as the oxidizing agent, the total amount of which is composed of the respective CMP The total amount of the substance is from 0.2 wt.% to 0.5 wt.%; (E) an aqueous medium; wherein the pH of the CMP composition (Q) is in the range of 7.1 to 9.

Z10: (A) colloidal or aerosol-like inorganic particles (A) or a mixture thereof, the total amount of which is 0.05 wt.% to 0.9 wt.%, based on the total weight of the respective CMP compositions; (B) at least one amine group The total amount of the acid is from 0.2 wt.% to 0.9 wt.% based on the total weight of the respective CMP compositions; (C) at least one corrosion inhibitor, the total amount of which is 0.008 based on the total weight of the respective CMP compositions Wt% to 0.02 wt.%; (D) hydrogen peroxide as an oxidizing agent, the total amount of which is 0.4 wt.% to 1.75 wt.% based on the total of the respective CMP compositions; (E) an aqueous medium; The pH of the CMP composition (Q) is in the range of 7.1 to 9.

Processes for preparing CMP compositions are generally known. These processes can be applied to prepare the CMP compositions of the present invention. This can be achieved by dispersing or dissolving the components (A), (B), (C), (D) and optionally the components (F) to (H) described above in an aqueous medium (E). (preferably water), and optionally by adjusting the pH by the addition of an acid, a base, a buffer or a pH adjuster. For this purpose, conventional and standard mixing processes and such as mixing vessels, high Mixing equipment for shear impellers, ultrasonic mixers, homogenizer nozzles or countercurrent mixers.

The polishing process is generally known and can be carried out by such processes and equipment under conditions commonly used for CMP in the fabrication of wafers having integrated circuits. There are no restrictions on the equipment that can be used to perform the grinding process.

As is known in the art, a typical apparatus for a CMP process consists of a rotating platen covered with a polishing pad. Orbital grinders are also used. The wafer is mounted on a carrier or chuck. The processed side of the wafer faces the polishing pad (single-sided polishing process). A retaining ring secures the wafer to a horizontal position.

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

To create a material loss, the wafer is pressed onto the polishing pad. Both the carrier and the platen are typically rotated about respective axes of rotation extending perpendicularly from the carrier and the platen. The rotating shaft of the carrier in rotation may remain fixed relative to the position of 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 speed of the carrier and the platen is generally (but not necessarily) set to a different value. During the CMP process of the present invention, the CMP composition of the present invention is typically applied to the polishing pad in a continuous stream or in a drop-wise manner. Usually, the platen temperature is set to a temperature of 10 ° C to 70 ° C.

The load on the wafer can be applied, for example, by a steel plate covered with a cushion (commonly referred to as a substrate film). If more advanced equipment is used, the wafer is pressed onto the mat using a flexible diaphragm loaded with air or nitrogen pressure. Since the downward pressure distribution on the wafer is more uniform than the downward pressure distribution of the carrier with the hard plate design, such a diaphragm carrier pair is used when a hard abrasive pad is used. It is better to use a low down force process. Carriers having the option of controlling the pressure distribution across the wafer can also be used in accordance with the present invention. It is typically designed to have a plurality of different chambers that can be loaded independently of each other to some extent.

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

By means of the CMP process of the invention and/or the use of the CMP composition of the invention, it is possible to obtain a surface region comprising cobalt or cobalt and copper and/or cobalt alloys or consisting of cobalt or cobalt and copper and/or cobalt alloys. A wafer of integrated circuits that has excellent functions.

The CMP composition of the present invention can be used as a ready-to-use slurry in a CMP process which has a long shelf life and exhibits a long-term stable particle size distribution. Therefore, it is easy to handle and store. It exhibits excellent grinding performance, especially by the combination of high material removal rate (MRR) of cobalt and low MRR of copper (or vice versa) to demonstrate a controllable and adjustable selectivity between cobalt and copper. Since the amount of its components is kept to a minimum, the CMP compositions according to the present invention can each be used in a cost effective manner.

Examples and comparative examples

The general procedure of the CMP experiment is described below.

Standard CMP process for 200mm Co/Co wafers: Strasbaugh nSpire (Model 6EC), ViPRR floating buckle carrier; downward pressure: 1.5 psi; back pressure: 1.0 psi; buckle pressure: 1.0 psi; grinding table/carrier speed: 130/127rpm; Slurry flow rate: 300 ml/min; grinding time: 15 s; (Co) 60 s; (Cu) polishing pad: Fujibo H800; substrate film: Strasbaugh, DF200 (136 holes); adjustment tool: Strasbaugh, soft brush, non-original Bits; each wafer is subsequently adjusted for subsequent processing by another wafer by sweeping twice with 5 lbs of downward force. The brush is soft. This means that the brush will not cause a significant removal rate to the soft pad even after 200 sweeps.

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

Stir the slurry in a local supply station.

The standard analysis procedure for (semi)metal-covered wafers is to determine the removal rate by the Sarto-rius LA310 S gauge or the NAPSON 4-point probe station by the difference in wafer weight before and after CMP.

The radial uniformity of the removal rate was evaluated by a 39 point diameter scan (range) using a NAP-SON 4-point probe station.

The standard consumables for CMP of metal film coated wafers are: Cu film: ECP (supplied by Ramco); Co film: 2000A PVD Co on Ti pads (supplier: ATMI); low k material: black diamond One generation (hereinafter referred to as "BD1"); the pH was measured with a pH combination electrode (Schott, Blue Line 22 pH electrode).

Standard Procedure for Slurry Preparation: A 4.2 wt.% aqueous solution of glycine was prepared by dissolving the desired amount of glycine in ultrapure water. After stirring for 20 min, the solution was neutralized by adding a 4.8 wt.% aqueous KOH solution and the pH was adjusted to pH 8.05 ± 0.1. Balanced water can be added to adjust the concentration. A 0.34 wt.% aqueous solution of BTA was prepared by dissolving the required amount of BTA in ultrapure water and stirring for 30 minutes until all solid BTA dissolved. By the amount of a desired surfactant (F) (e.g. the Triton ^TM DF 16 from Dow) were dissolved in ultrapure water for 30 minutes to prepare 1wt.% Nonionic surfactant stock solution.

To prepare the CMP slurry of the examples, the glycine acid (amino acid (B)) solution, the BTA (corrosion inhibitor (C)) solution and the surfactant (F) solution were mixed and the colloidal state was added under continuous stirring. A cerium oxide particle solution (30% stock solution of (A), such as Fuso ^® PL 3). After the addition of the required amount of the abrasive (A) was completed, the dispersion was stirred for an additional 5 minutes. The pH was then adjusted to 8.3 ± 0.1 by the addition of a 4.8 wt.% aqueous KOH solution. Equilibrium water was added under stirring to adjust the concentration of the CMP slurry to the values listed in Tables 2, 3, 4, and 5 of the following examples and comparative examples. 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 min to 15 min).

Slurry of Comparative Examples V3, V4, V5 and V6 was prepared according to a modified version of the standard stock preparation procedure. A slurry according to standard procedures was prepared but without BTA (C). The necessary amount of BTA (C) (1% stock solution) was then added with stirring. The required amount of H ₂ O ₂ (D) was added immediately before the slurry was used for CMP (1 min to 15 min).

The slurries of Comparative Examples V7 through V15 were prepared by a modified version of the standard stock preparation procedure. 450 g of Fuso ^® PL3 cerium (A) dispersion (20.0%) was added to 1550 g of the slurry prepared according to the standard preparation procedure under stirring to obtain 4.9% cerium oxide, 80 ppm BTA (C), 0.58% gan. alanine ^{(B), 0.023% Triton TM} DF16 (F), pH of the slurry was 7.9. The required amount of H ₂ O ₂ (D) was added immediately before the slurry was used for CMP (1 min to 15 min).

Inorganic particles used in the examples (A)

Cocoon-shaped colloidal particles of silicon dioxide having an average primary particle size (d1) of 35nm and an average secondary particle diameter (d2) to 70nm (measured using dynamic light scattering techniques via Horiba Instruments) of (e.g. Fuso ^® PL-3).

Particle shape characterization program

An aqueous crucible ceria particle dispersion having a solids content of 20 wt.% was dispersed on a carbon foil and dried. The dried dispersion was analyzed by energy filtration-transmission electron microscopy (EF-TEM) (120 kV) and scanning electron microscopy secondary electron image (SEM-SE) (5 kV). An EF-TEM image (Fig. 4) with a resolution of 2k, 16 bits, and 0.6851 nm/pixel was used for this analysis. The image is binary coded with a threshold after noise suppression. Then manually separate the particles. Overlying particles and edge particles are discerned and are not used for this analysis. The ECD, form factor, and sphericity as previously defined are calculated and statistically classified.

If present, an amphiphilic nonionic polyoxyethylidene-polyoxypropylpropyl ether surfactant is used as the surfactant (F), which is an alkyl group having an average of 6 to 12 carbon atoms. molecular oxygen stretch mixture of propylene monomer units (e.g., Triton ^TM DF from the DOW 16) 1-5 and 2-10 showed a random distribution of oxygen monomer units and extending ethyl.

Seen in Figure 5, the material removal rate is highly correlated with the concentration of H ₂ O _2. For the copper material removal rate, the three types of regions can be defined by the correlation with the H ₂ O ₂ concentration. In the range of 0 wt.% to 0.1 wt.% H ₂ O ₂ , the copper removal rate is extremely low and is not affected by the increase in H ₂ O ₂ concentration. The copper removal rate increases in the range of 0.2 wt.% to 0.5 wt.% H ₂ O ₂ . In the range of 0.5 wt.% to 2.0 wt.% H ₂ O ₂ , the copper removal rate is independent of the increase in H ₂ O ₂ concentration. In contrast thereto, the cobalt removal rate has increased with an extremely low H ₂ O ₂ concentration of at least 0.05 wt.%. The cobalt removal rate reached a maximum at 0.4 wt.% H ₂ O ₂ and then decreased. This surprising discovery of a dependency-based, cobalt and copper, may be selectively changed easily by H ₂ O ₂ concentration is adjusted.

The change in corrosion inhibitor concentration (C) (e.g., BTA) exhibits a strong influence on the removal rate of cobalt and copper materials.

Table 4: CMP compositions of Comparative Examples V7 to V15 having high particle (A) concentrations and different H ₂ O ₂ (D) concentrations, the pH of such compositions in the CMP process using such compositions and Material removal rate (MRR) and selectivity data, wherein the aqueous medium (E) is ultrapure water (wt.%=% by weight)

At high particle (A) concentrations, the correlation of the copper removal rate to the H ₂ O ₂ (D) concentration is different from the previously mentioned case at the low particle (A) concentration according to the present invention. The copper removal rate shows a significant maximum (see Figure 6). Selectivity control of cobalt and copper is not possible at high particle (A) concentrations.

Table 5: CMP composition of Example 12 and Comparative Examples V16 to V17, pH and material removal rate (MRR) data in a CMP process using such compositions under different downward pressures Where the aqueous medium (E) is ultrapure water (wt.% = weight percent)

The copper removal rate is increased in a linear fashion by increasing the downward pressure. In contrast, a linear increase in downward pressure results in an exponential increase in the removal rate of cobalt material (see Figure 7). In order to have a controllable process in terms of cobalt material removal rate, a low downforce system in accordance with the present invention is advantageous.

The CMP compositions according to Examples 1 to 12 of the present invention exhibit high cobalt removal rates of cobalt and copper, high cobalt removal rates at low abrasive (A) concentrations, and low k materials (eg, black diamond first generation (BD1) )) Improved performance in terms of low material removal rate; low etch behavior and high dispersion stability. The selectivity can be increased by up to 41 factors by using the CMP composition according to the invention. By varying the amount of H ₂ O ₂ (D) at low particle (A) concentrations, the selectivity can be adjusted over a wide range.

Claims (14)

A chemical mechanical polishing (CMP) composition (Q) comprising: (A) colloidal or aerosol-like inorganic particles (A) or a mixture thereof, the total amount of which is 0.0001 wt% based on the total weight of the respective CMP compositions. % to 2.5 wt.%; (B) at least one amino acid in a total amount of 0.2 wt.% to 1 wt.% based on the total weight of the respective CMP compositions; (C) at least one corrosion inhibitor, The total amount is 0.001 wt.% to 0.02 wt.% based on the total weight of the respective CMP compositions; (D) hydrogen peroxide as the oxidizing agent, the total amount of which is 0.0001 wt% based on the total of the respective CMP compositions. .% to 2 wt.%; (E) an aqueous medium; wherein the pH of the CMP composition (Q) is in the range of 6 to 9.5. The CMP composition (Q) of claim 1, wherein the inorganic particles (A) are colloidal particles. The CMP composition (Q) of claim 1, wherein the inorganic particles (A) are aerosol particles. The CMP composition (Q) according to any one of claims 1 to 3, wherein the inorganic particles (A) are cerium oxide particles. The CMP composition (Q) according to any one of claims 1 to 4, wherein the average particle size of the particles (A) is 20 nm to 200 nm as measured by a dynamic light scattering technique. The CMP composition (Q) according to any one of claims 1 to 5, wherein the at least one amino acid (B) is selected from the group consisting of glycine, arginine, and amine acid, Alanine, leucine, valine, histidine, cysteine, serine and proline. The CMP composition (Q) according to any one of claims 1 to 6, wherein the at least one corrosion inhibitor (C) is selected from the group consisting of benzotriazole, methyl-benzo Triazole and 1,2,4 triazole. The CMP composition (Q) according to any one of claims 1 to 7, which comprises a total amount of at least 0.001 wt.% to 0.05 wt.%, based on the total weight of the respective CMP compositions. A surfactant (F). The CMP composition (Q) according to any one of claims 1 to 8, wherein the at least one surfactant (F) is a two-enhanced nonionic surfactant comprising a polyoxyalkylene group. . A use of the CMP composition (Q) according to any one of claims 1 to 9 for chemical mechanical polishing of a substrate (S) used in the semiconductor industry, wherein the substrate (S) comprises : (i) cobalt, or; (ii) cobalt and copper, and / or (iii) cobalt alloy. A method of fabricating a semiconductor device comprising containing cobalt or cobalt and copper and/or cobalt alloys or in the presence of a CMP composition (Q) as defined in any one of claims 1 to 9 The substrate of the surface region composed of cobalt or cobalt and copper and/or cobalt alloy is subjected to chemical mechanical polishing. The method of claim 11, wherein the chemical mechanical polishing of the substrate is carried out at a downward pressure of 13.8 kPa (2 psi) or less. The method of any one of clauses 11 to 12, wherein the selectivity of cobalt and copper material removal rate is in the range of 0.1 to 50. The method of claim 11, wherein the hydrogen peroxide concentration is varied during the grinding method.