WO2016008896A1 - Composition de polissage mécano-chimique (cmp) - Google Patents

Composition de polissage mécano-chimique (cmp) Download PDF

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Publication number
WO2016008896A1
WO2016008896A1 PCT/EP2015/066086 EP2015066086W WO2016008896A1 WO 2016008896 A1 WO2016008896 A1 WO 2016008896A1 EP 2015066086 W EP2015066086 W EP 2015066086W WO 2016008896 A1 WO2016008896 A1 WO 2016008896A1
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WIPO (PCT)
Prior art keywords
cmp composition
cobalt
cmp
composition
total amount
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PCT/EP2015/066086
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English (en)
Inventor
Robert REICHARDT
Max SIEBERT
Yongqing Lan
Michael Lauter
Haci Osman GUEVENC
Julian PRÖLSS
Sheik Ansar Usman Ibrahim
Reza Golzarian
Original Assignee
Basf Se
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Application filed by Basf Se filed Critical Basf Se
Priority to US15/325,464 priority Critical patent/US10570316B2/en
Priority to EP15736840.8A priority patent/EP3169737B1/fr
Priority to JP2017502617A priority patent/JP6817186B6/ja
Priority to CN201580037575.3A priority patent/CN106661382B/zh
Priority to KR1020177003150A priority patent/KR102501836B1/ko
Priority to SG11201700255UA priority patent/SG11201700255UA/en
Publication of WO2016008896A1 publication Critical patent/WO2016008896A1/fr
Priority to IL249516A priority patent/IL249516B/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions

Definitions

  • a chemical mechanical polishing (CMP) composition Description This invention essentially relates to a chemical mechanical polishing (CMP) composition and its use in polishing substrates of the semiconductor industry comprising cobalt or cobalt and copper and /or a cobalt alloy.
  • the CMP composition according to the invention comprises inorganic particles, at least one amino acid, at least one corrosion inhibitor, hydrogen peroxide and aqueous medium.
  • the CMP composition shows an improved and adjustable polishing performance.
  • CMP chemical mechanical polishing
  • CMP chemical mechanical polishing
  • CMP composition also referred to as CMP composition or CMP slurry.
  • Mechanical action is usually carried out by a polishing pad which is typically pressed onto the to-be- polished surface and mounted on a moving platen. The movement of the platen is usually linear, rotational or orbital.
  • a rotating wafer holder brings the to-be-polished wafer in contact with a polishing pad.
  • the CMP composition is usually applied between the to-be-polished wafer and the polishing pad.
  • the size of the copper interconnect structure is getting smaller and smaller.
  • the thickness of barrier or adhesion layer in the copper interconnect structure is get- ting thinner.
  • the traditional copper barrier/adhesion layer stack Ta/TaN is not suitable any more, as the resistivity of Ta is relatively high and copper cannot be directly electroplated onto Ta. Compared with Ta, cobalt has lower resistivity and is cheaper.
  • the adhesion between Cu and Co is good. Cu can easily nucleate on Co, also copper can be directly electroplated on cobalt.
  • Co is used as adhesion or barrier layer for copper interconnects, while Co can also be used as nano-crystalline Co in memory device and as metal gate in MOSFET.
  • Porous low k dielectrics material has been already used in the current interconnect structures. It is reported that low k material can be easily damaged by plasma or polishing slurries. In current chemical mechanical polishing processing, to reduce the damage to low-k dielectrics, most of the current slurries used for copper and barriers are acidic. But it is observed that copper and cobalt easily suffered from dissolution in acidic solution containing oxidant for example hydro- gen peroxide. This makes the polishing rate of copper and cobalt too high so that it will induce the dishing of copper lines. In addition the dissolution of the cobalt adhesion layer on the side- wall of the copper interconnect structure can lead to the delamination of copper lines and cause reliability problems.
  • CMP compositions comprising inorganic particles, at least one amino acid, at least one corrosion inhibitor, hydrogen peroxide and water and its use in polishing substrates of the semiconductor industry comprising cobalt and or copper are known and de- scribed, for instance, in the following references.
  • US 2013/0140273 A1 discloses a slurry for chemical mechanical polishing of Co.
  • the slurry- comprises 0.01 -2 % inhibitor, 0-5 % oxidant, 0.1 -10 % abrasive, 0.001 -10 % complexing agent, and water.
  • the pH value of the slurries is adjusted to 3-5 by a pH value adjustor.
  • the inhibitor is chosen from one or more kinds of five-membered heterocycle compounds containing S and N atoms.
  • the oxidant is one or more chosen from H2O2, (NH4)2S208, KIO4, and KCIO5.
  • the abrasive is one or more chosen from S1O2, Ce02, and AI2O3.
  • the complexing agent is one or more chosen from amino acid and citric acid.
  • One of the objects of the present invention was to provide a CMP composition appropriate for the CMP of cobalt or cobalt and copper and /or a cobalt alloy comprising substrates and show- ing an improved polishing performance, particularly a controllable and adjustable selectivity between cobalt and copper. Furthermore, a CMP composition was sought that suppresses the corrosion of cobalt and copper, leads to high material removal rates, is compatible with the low k dielectric materials of the semiconductor substrates, gives a high quality surface finish, decreases dishing, is storage stable and would be ready-to-use in neutral to alkaline pH range. Furthermore, a respective CMP process was to be provided. Accordingly, a CMP composition was found which comprises
  • CMP composition (Q) has a pH in the range of from 6 to 9.5.
  • a process for the manufacture of a semiconductor device comprising the chemical mechanical polishing of a substrate comprising a surface region containing or consisting of cobalt or cobalt and copper and/or of a cobalt alloy in the presence of said chemical mechanical polishing (CMP) composition (Q).
  • CMP chemical mechanical polishing
  • the CMP composition (Q) according to the invention is showing an exceptional dependence of the copper material removing rate on the hydrogen peroxide concentration and therewith gives the opportunity to adjust the selectivity of cobalt to copper by varying the H2O2 concentration. Without being bound to this theory it is presently believed that this is due to the combination of a low abrasive concentration below 2.5 wt.% and a pH in the range of from 6 to 9.5.
  • the CMP composition comprises colloidal or fumed inorganic particles or a mixture thereof (A).
  • colloidal inorganic particles are inorganic particles which are produced by a wet precipitation process; fumed inorganic particles are produced by high temperature flame hydrolysis of for example metal chloride precursor with hydrogen in the presence of oxygen, for example using the Aerosil ® process.
  • 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). Preferably not more than 2.0 wt.%, most preferably not more than 1 .5 wt.%, particularly not more than 0.8 wt.%, based on the total weight of the composition (Q).
  • 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.%, particularly at least 0.3 wt.%, based on the total weight of the composition (Q).
  • the amount of (A) can be in the range of from 0.4 wt.% to 1 .2 wt.%.
  • the particles (A) can be contained in the composition (Q) in various particle size dis- tributions.
  • the particle size distribution of the particles (A) can be monomodal or multimodal. In case of multimodal particle size distribution, bimodal is often preferred. In order to have an easily reproducible property profile and easily reproducible conditions during the CMP process of the invention, a monomodal particle size distribution may be preferred for the particles (A). Often it is most preferred for the particles (A) to have a monomodal particle size distribution.
  • particle size distribution the particles (A) may have is not particularly limited.
  • the mean particle size of the particles (A) can vary within a wide range.
  • the mean particle size is the deo 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.
  • DLS dynamic light scattering
  • SLS static light scattering
  • DLS dynamic light scattering measurement according to manual
  • a Horiba LB-550 V DLS, dynamic light scattering measurement according to manual
  • the particle size distribution of the fumed or colloidal inorganic particle dispersion (A) is usually measured in a plastic cuvette at 0.1 to 1 .0 % solid concentration and dilution, if necessary, is carried out with the dispersion medium or ultra-pure water.
  • the mean particle size of the particles (A) is in the range of from 20 to 200 nm, more preferably in the range of from 25 to 180 nm, most preferably in the range of from 30 to 170 nm, particularly preferably in the range of from 40 to 160 nm, and in particular in the range of from 45 to 150 nm, as measured with dynamic light scattering techniques using instruments for example a High Performance Particle Sizer (HPPS) from Malvern Instruments, Ltd. or Horiba LB550.
  • HPPS High Performance Particle Sizer
  • the BET surface determined according to DIN ISO 9277:2010-09 of the particles (A) can vary within a wide range.
  • the BET surface of the particles (A) is in the range of from 1 to 500 m 2 /g, more preferably in the range of from 5 to 250 m 2 /g, most preferably in the range of from 10 to 100 m 2 /g, in particular in the range of from 20 to 90 m 2 /g, for example in the range of from 25 to 85 m 2 /g.
  • the particles (A) can be of various shapes. Thereby, the particles (A) may be of one or essentially only one type of shape. However, it is also possible that the particles (A) have different shapes. For instance, two types of differently shaped particles (A) may be present.
  • (A) can have the shape of cubes, cubes with bevelled edges, octahedrons, icosahedrons, cocoons, nodules or spheres with or without protrusions or indentations. Preferably, they are essentially spherical, whereby typically these have protrusions or indentations. It may be prefered that, the inorganic particles (A) are cocoon-shaped.
  • Cocoon-shaped particles are particles with a minor axis of from 10 to 200 nm, a ratio of major/minor axis of 1 .4 to 2.2, more preferably of 1 .6 to 2.0.
  • they Preferably they have an averaged shape factor of from 0.7 to 0.97, more preferably of from 0.77 to 0.92, preferably an averaged sphericity of from 0.4 to 0.9, more preferably of from 0.5 to 0.7 and preferably an averaged equivalent circle diameter of from 41 to 66 nm, more preferably of from 48 to 60 nm, which can be determined by transmission electron microscopy and scanning electron microscopy.
  • the determination of the shape factor, the sphericity and the equivalent circle diameter of cocoon-shaped particles is explained hereinbelow with reference to figures 1 to 4.
  • the shape factor gives information on the shape and the indentations of an individual particle (see figure 1 ) and can be calculated according to the following formula:
  • shape factor 4 ⁇ (area / perimeter 2 )
  • the shape factor of a spheric particle without indentations is 1.
  • the value of shape factor decreases when the number of indentations increases.
  • the sphericity gives information on the elongation of an individual particle using the moment about the mean and can be calculated according to the following formula wherein M are the centres of gravity of the respective particle:
  • the sphericity of a spheric particle is 1.
  • the value of the sphericity decreases when particles are elongated.
  • the equivalent circle diameter (also abbreviated as ECD in the following) of an individual non- circular particle gives information on the diameter of a circle which has the same area as the respective non-circular particle (see figure 3).
  • the averaged shape factor, averaged sphericity and averaged ECD are the arithmetic averages of the respective property related to the analyzed number of particles.
  • the procedure for particle shape characterization is as follows. An aqueous cocoon-shaped silica particle dispersion with 20 wt.% solid content is dispersed on a carbon foil and is dried. The dried dispersion is analyzed by using Energy Filtered-Transmission Electron Microscopy (EF-TEM) (120 kilo volts) and Scanning Electron Microscopy secondary electron image (SEM- SE) (5 kilo volts). The EF-TEM image (see figure 4) having a resolution of 2k, 16 Bit, 0.6851 nm/pixel is used for the analysis. The images are binary coded using the threshold after noise suppression. Afterwards the particles are manually separated. Overlying and edge particles are discriminated and not used for the analysis. ECD, shape factor and sphericity as defined before are calculated and statistically classified.
  • EF-TEM Energy Filtered-Transmission Electron Microscopy
  • SEM- SE Scanning Electron Microscopy secondary electron image
  • cocoon-shaped particles may be FUSO ® PL-3 manufactured by Fuso Chemical Corporation having an average primary particle size (d1 ) of 35 nm and an average secondary particle size (d2) of 70 nm.
  • the chemical nature of particles (A) is not particularly limited.
  • (A) may be of the same chemical nature or a mixture of particles of different chemical nature. As a rule, particles (A) of the same chemical nature are preferred.
  • (A) can be
  • - inorganic particles such as a metal, a metal oxide or carbide, including a metalloid, a metalloid oxide or carbide, or
  • the particles (A) are colloidal or fumed inorganic particles or a mixture thereof.
  • oxides and carbides of metals or metalloids are preferred. More preferably, particles (A) are alumina, ceria, copper oxide, iron oxide, nickel oxide, manganese oxide, silica, silicon nitride, silicon carbide, tin oxide, titania, titanium carbide, tungsten oxide, yttrium oxide, zirconia, or mixtures or composites thereof. Most preferably, particles (A) are alumina, ceria, silica, titania, zirconia, or mixtures or composites thereof. In particular, particles (A) are silica. For example, particles (A) are colloidal silica.
  • colloidal silica refers to silicon dioxide that has been prepared by condensation polymerization of Si(OH)4 .
  • the precursor Si(OH)4 can be obtained, for example, by hydrolysis of high purity alkoxysilanes, or by acidification of aqueous silicate solutions.
  • colloidal silica can be prepared in accordance with U.S. Pat. No. 5,230,833 or can be obtained as any of various commercially available products, such as the Fuso ® PL-1 , PL-2, and PL-3 products, and the Nalco ® 1050, 2327 and 2329 products, as well as other similar products available from DuPont, Bayer, Applied Research, Nissan Chemical or Clariant.
  • the CMP composition comprises at least one amino acid (B).
  • amino acids organic compounds that have an amino group and an acid group are referred to as amino acids.
  • amino acids all individual stereoisomers and racemic mixtures thereof are also contemplated for the amino acids.
  • both the amino and the acid groups are attached to one carbon (termed as alpha-amino carboxylic acids) are used as the chemical additive in the CMP slurry.
  • alpha-amino carboxylic acids are known and there are twenty "natural" amino acids which are used as basic components of proteins in living organisms.
  • the amino acids can be hydrophilic, neutral or hydrophobic depending on their side chains in presence of an aqueous carrier.
  • the addition of alpha amino acid as polishing additive may increase the metal material removal rates
  • the at least one alpha-amino acid (B) may be represented by the formula (I) H 2 N-CR 1 R 2 COOH (I) wherein R 1 and R 2 are independently from each other hydrogen, cyclic, branched and straight chain moieties having from 1 to 8 carbon atoms that are unsubstituted or substituted with one or more substituents selected from nitrogen containing substituents, oxygen containing substitu- ents and sulfur containing substituents including but not limited to -COOH, -CONH2, -NH2, -S-, - OH, -SH, and mixtures and salts thereof.
  • the at least one amino acid (B) is alpha-alanine, arginine, aspartic acid, cystine, cys- teine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, and mixtures and salts thereof. More preferably (B) is alpha-alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, leucine, lysine, proline, serine, valine, and mixtures and salts thereof.
  • (B) is alpha-alanine, aspartic acid, glutamic acid, glycine, proline, serine, and mixtures and salts there- of, particularly (B) is alpha-alanine, aspartic acid, glycine and mixtures and salts thereof, for example (B) is glycine.
  • 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 not more than 0.9 wt.%, most preferably not more than 0.85 wt.%, particularly not more than 0.8 wt.%, based on the total weight of the composition (Q).
  • the amount of (B) is at least 0.2 wt.% based on the total weight of the composition (Q). Preferably at least 0.3 wt.%, more preferably at least 0.4 wt.%, most preferably at least 0.5 wt.%, particularly at least 0.6 wt.%, based on the total weight of the composition (Q).
  • the amount of (B) can be in the range of from 0.65 wt.% to 0,78 wt.%.
  • the CMP composition (Q) comprises at least one corrosion inhibitor.
  • two corrosion inhibitors may be comprised in the CMP composition (Q).
  • a corrosion inhibitor is a compound that can protect the surface of a metal, e.g. copper by forming a protective molecular layer on the metal surface.
  • Corrosion inhibitors (C) can for instance be diazoles, triazoles, tetrazoles and their derivatives.
  • the at least one corrosion inhibitor (C) may for example be 1 ,2,4 triazole, 1 ,2,3 tria- zole, 3-amino-methyl-1 H-1 ,2,4-triazole, benzotriazole, 4-methyl benzotriazole, 5-methyl benzotriazole, 5-6-dimethyl benzotriazole, 5-chloro benzotriazole, 1 -octanyl benzotriazole, carboxy- benzotriazole, butyl-benzotriazole, 6-ethyl-1 H-1 ,2,4 benzotriazole, (1 -pyrrolidinyl methyl) benzotriazole, 1 -n-butyl-benzotriazole, benzotriazole-5-carboxylic acid, 4,5,6,7-tetrahydro-1 H- benzotriazole, imidazole,
  • 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).
  • 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.%, particularly at least 0.008 wt.%, based on the total weight of the composi- tion (Q).
  • the amount of (C) can be in the range of from 0.009 wt.% to 0.012 wt.%.
  • the CMP composition (Q) comprises hydrogen peroxide (D) as oxidizing agent.
  • the oxidizing agent is a compound which is capable of oxidizing the to-be-polished substrate or one of its layers.
  • 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.%, most prefer- ably not more than 1 .3 wt.%, particularly not more than 1 .2 wt.%, based on the total weight of the composition (Q).
  • 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.%, particularly at least 0.2 wt.%, based on the total weight of the composition (Q).
  • the amount of (D) can be in the range of from 0.02 wt.% to 0.1 wt.%, of from 0.15 wt.% to 0.8 wt.%, of from 0.8 wt.% to 1 .9 wt.%, based on the total weight of the composition (Q).
  • the CMP composition comprises an aqueous medium (E).
  • E can be of one type or a mixture of different types of aqueous media.
  • the aqueous medium (E) can be any medium which contains water.
  • the aqueous medium (E) is a mixture of water and an organic solvent miscible with water (e.g. an alcohol, preferably a Ci to C3 alcohol, or an alkylene glycol derivative). More preferably, the aqueous medium (E) is water. Most preferably, the aqueous medium (E) is de-ionized water. If the amounts of the components other than (E) are in total x % by weight of the CMP composition, then the amount of (E) is (100-x) % by weight of the CMP composition (Q).
  • the properties of the CMP composition according to the invention respectively may depend on the pH of the corresponding composition.
  • the CMP composition (Q) has a pH in the range of from 6 to 9.5.
  • the pH value of the compositions used or according to the invention respectively is in the range of from 6.8 to 9.2, more preferably from 7 to 8.8, most preferably from 7.3 to 8.7, particularly preferably from 7.5 to 8.5, for example from 7.6 to 8.4.
  • the CMP composition (Q) of the invention can further optionally contain at least one non-ionic surfactant (F).
  • a surfactant used in a CMP composition is a surface-active compound which de- creases the surface tension of a liquid, the interfacial tension between two liquids, or that between a liquid and a solid.
  • any non-ionic surfactant (F) can be used.
  • the non-ionic surfactant (F) is preferably water-soluble and/or water-dispersible, more preferably water-soluble.
  • Water-soluble means that the relevant component or ingredient of the composition of the invention can be dissolved in the aqueous phase on the molecular level.
  • Water- dispersible means that the relevant component or ingredient of the composition of the invention can be dispersed in the aqueous phase and forms a stable emulsion or suspension.
  • the non-ionic surfactant (F) is preferably an amphiphilic non-ionic surfactant, i.e. a surfactant which comprises at least one hydrophobic group (b1 ) and at least one hydrophilic group (b2).
  • a surfactant which comprises at least one hydrophobic group (b1 ) and at least one hydrophilic group (b2).
  • the nonionic surfactant (F) can comprise more than one hydrophobic group (b1 ), e.g., 2, 3 or more groups (b1 ), which are separated from each other by at least one hydro- philic group (b2) as hereinbelow described.
  • nonionic surfactant (F) can comprise more than one hydrophilic group (b2), e.g., 2, 3 or more groups (b2) which are separated from each other by hydrophobic groups (b1 ) as hereinbelow described.
  • the nonionic surfactant (F) can have different blocklike general structures.
  • Examples of such general blocklike structures are: b1 -b2,
  • the non-ionic surfactant (F) is more preferably an amphiphilic non-ionic surfactant comprising a polyoxyalkylene group.
  • the hydrophobic group (b1 ) is preferably an alkyl group, more preferably an alkyl group having 4 to 40, most preferably 5 to 20, particularly preferably 7 to 18, in particular 10 to 16, for example 1 1 to 14 carbon atoms.
  • the hydrophilic group (b2) is preferably a polyoxyalkylene group. Said 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 comprising
  • the hydrophilic group (b2) is a hydrophilic group selected from the group consisting of polyoxyalkylene groups comprising
  • the oxyalkylene monomer units other than oxyethylene monomer units (b22) are substituted oxyalkylene monomer units wherein the substituents are selected from the group consisting of alkyl, cycloalkyi, aryl, alkyl-cycloalkyi, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl- aryl groups.
  • the oxyalkylene monomer units other than oxyethylene monomer units (b22) are more preferably derived from substituted oxiranes (X) wherein the substituents are select- ed from the group consisting of alkyl, cycloalkyi, aryl, alkyl-cycloalkyi, alkyl-aryl, cycloalkyl- aryl and alkyl-cycloalkyl-aryl groups,
  • - for example derived from methyl oxirane (propyleneoxide) and/or ethyl oxirane (butylene oxide).
  • the substituents of the substituted oxiranes (X) themselves can also carry inert substituents, i.e., substituents which do not adversely affect the copolymerization of the oxiranes (X) and the surface activity of the non-ionic surfactants (F).
  • inert substituents are fluorine and chlorine atoms, nitro groups and nitrile groups. If such inert substituents are present, they are used in such amounts that they do not adversely affect the hydrophilic-hydrophobic balance of the non-ionic surfactant (F).
  • the substituents of the substituted oxiranes (X) do not carry such inert substituents.
  • the substituents of the substituted oxiranes (X) are preferably selected from the group consist- ing of alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms in spirocyclic, exocyclic and/or annealed configuration, aryl groups having 6 to 10 carbon atoms, alkyl-cycloalkyl groups having 6 to 20 carbon atoms, alkyl-aryl groups having 7 to 20 carbon atoms, cycloalkyl-arylgroup 1 1 to 20 carbon atoms, and alkyl-cycloalkyl-aryl groups having 12 to 30 carbon atoms.
  • the substituents of the substituted oxiranes (X) are selected from the group consisting of alkyl groups having 1 to 10 carbon atoms. Particularly, the substituents of the substituted oxiranes (X) are selected from the group consisting of alkyl groups having 1 to 6 carbon atoms.
  • Examples for the most preferred substituted oxiranes (X) are methyl oxirane (propyleneoxide) and/or ethyl oxirane (butylene oxide), particularly methyl oxirane.
  • the hydrophilic group (b2) consists of the monomer units (b21 ) and (b22).
  • the hydrophilic group (b2) is preferably a polyoxyethylene, polyoxypro- pylene or polyoxybutylene group, more preferably a polyoxyethylene group.
  • the hydrophilic group (b2) comprises or consists of the monomer units (b21 ) and (b22)
  • the polyoxyalkylene group - acting as hydrophilic group (b2) - contains the monomer units (b21 ) and (b22) in random, alternating, gradient and/or blocklike distribution.
  • one hydrophilic group (b2) can have only one type of distribution, i.e., random : ...-b21 -b21 -b22-b21 -b22-b22-b22-b21 -b22-... ;
  • the hydrophilic group (b2) can also contain at least two types of distributions, e.g., an oligomeric or polymeric segment having a random distribution and an oligomeric or polymeric segment having alternating distribution. Most preferably, the hydrophilic group (b2) preferably has only one type of distribution, and most preferably, said distribution is random or blocklike.
  • the molar ratio of (b21 ) to (b22) can vary broadly and, therefore, can be adjusted most advantageously to the particular requirements of the composition, the process and the use of the invention.
  • the molar ratio (b21 ):(b22) is 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 particularly, from 15:1 to 2:1 , and for example, from 9:1 to 2:1.
  • the degree of polymerization of the oligomeric and polymeric polyoxyalkylene groups - acting as hydrophilic groups (b2) - can vary broadly and, therefore, can be adjusted most advantageously to the particular requirements of the composition, the process and the use of the invention.
  • the degree of polymerization is in the range of from 5 to 100, preferably 5 to 90, and most preferably, 5 to 80.
  • the non-ionic surfactant (F) is an amphiphilic non-ionic polyoxyethylene- polyoxypropylene alkyl ether surfactant which is a mixture of molecules containing, on the average, an alkyl group having 10 to 16 carbon atoms and 5 to 20 oxyethylene monomer units (b21 ) and 2 to 8 oxypropylene monomer units in random distribution.
  • the non-ionic surfactant (F) is an amphiphilic non-ionic polyoxyethylene-polyoxypropylene alkyl ether surfactant which is a mixture of molecules containing, on the average, an alkyl group having 1 1 to 14 carbon atoms and 12 to 20 oxyethylene monomer units and 3 to 5 oxypropylene monomer units in random distribution.
  • the non-ionic surfactant (F) if present can be contained in varying amounts in the CMP composition (Q).
  • 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.%, particularly not more than 0.1 wt.%, for example not more than 0.05 wt.%, based on the total weight of the composition (Q).
  • 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.%, particularly at least 0.005 wt.%, for example at least 0.008 wt.%, based on the total weight of the composition (Q).
  • the non-ionic 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, particularly at least 800, for example at least 900.
  • the weight average molecular weight of (F) is preferably not more than 15,000, more preferably not more than 6,000, most preferably not more than 3,000, particularly not more than 2,000, for example not more than 1 ,400 [g/mol], as determined by gel permeation chromatography (abbreviated as "GPC” in the following).
  • the weight average molecular weight of (F) is from 900 to 1 ,400 [g/mol] as determined by GPC.
  • GPC gel permeation chromatography
  • the solubility of (F) in water at pH 7 at 25°C under atmospheric pressure is preferably at least 1 g/L, more preferably at least 5 g/L, most preferably at least 20 g/L, particularly at least 50 g/L, for example at least 150 g/L. Said solubility can be determined by evaporating the solvent and measuring the remaining mass in the saturated solution.
  • the CMP composition of the invention can further optionally contain at least one additional complexing agent (G) different from the at least one amino acid (B), for example one complex- ing agent.
  • the complexing agent is a compound which is capable of complexing the ions of the to-be-polished substrate or of one of its layers.
  • (G) is a carboxylic acid having at least one COOH groups, an N-containing carboxylic acid, N-containing sulfonic acid, N-containing sulfuric acid, N-containing phosphonic acid, 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.
  • the at least one additional complexing agent (G) can be acetic acid, gluconic acid, lactic acid, nitriloacetic acid, ethylenediaminetet- raacetic 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.
  • EDTA ethylenediaminetet- raacetic acid
  • the complexing agent (G) can be contained in varying amounts.
  • the amount of (G) is not more than 20 wt.%, more preferably not more than 10 wt.%, most preferably not more than 5 wt.%, for example not more than 2 wt.%, based on the total weight of the corresponding composition.
  • 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 invention can further optionally contain at least one biocide (H), for example one biocide.
  • the biocide is a compound which deters, renders harmless, or exerts a controlling effect on any harmful organism by chemical or biological means.
  • (H) is an quaternary ammonium compound, an isothiazolinone-based compound, an N- substituted diazenium dioxide, or an N'-hydroxy-diazenium oxide salt. More preferably, (H) is an N-substituted diazenium dioxide, or an N'-hydroxy-diazenium oxide salt. If present, the biocide (H) can be contained in varying amounts.
  • 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.%, particularly not more than 0.02 wt.%, for example not more than 0.008 wt.%, based on the total weight of the corresponding composition. 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.%, particularly at least 0.003 wt.%, for example at least 0.006 wt.%, based on the total weight of the corresponding composition.
  • the CMP compositions according to the invention respectively may also contain, if necessary, various other additives, including but not limited to pH adjusting agents, stabilizers etc.
  • Said other additives are for instance those commonly employed in CMP compositions and thus known to the person skilled in the art.
  • Such addition can for example stabilize the dispersion, or improve the polishing performance, or the selectivity between different layers.
  • said additive can be contained in varying amounts.
  • the amount of said additive is not more than 10 wt.%, more preferably not more than 1 wt.%, most preferably not more than 0.1 wt.%, for example not more than 0.01 wt.%, based on the total weight of the corresponding composition.
  • the amount of said additive is at least 0.0001 wt.%, more preferably at least 0.001 wt.%, most preferably at least 0.01 wt.%, for example at least 0.1 wt.%, based on the total weight of the corresponding composition.
  • a semiconductor device can be manufactured by a process which comprises the CMP of a sub- strate in the presence of the CMP composition of the invention.
  • said process comprises the CMP of a substrate comprising a surface region containing or consisting of cobalt or cobalt and copper and / or of a cobalt alloy.
  • the semiconductor device which can be manufactured by the process according to the invention is not particularly limited.
  • the semiconductor devices can be an electronic component comprising semiconducting materials, as for example silicon, germanium, and lll-V materials.
  • Semiconductor devices can be those which are manufactured as single discrete devices or those which are manufactured as integrated circuits (ICs) consisting of a number of devices manufactured and interconnected on a wafer.
  • Semiconductor devices can be two ter- minal devices for example a diode, three terminal devices for example a bipolar transistor, four terminal devices for example a Hall effect sensor or multi-terminal devices.
  • said semiconductor device is a multi-terminal device.
  • Multi-terminal devices can be logic devices as integrated circuits and microprocessors or memory devices as random access memory (RAM), read only memory (ROM) and phase change random access memory (PCRAM).
  • RAM random access memory
  • ROM read only memory
  • PCRAM phase change random access memory
  • said semiconductor device is a multi-terminal logic device.
  • said semiconductor device is an integrated circuit or microprocessor.
  • Co is used as adhesion or barrier layer for copper interconnects.
  • Co is contained for example in memory devices and as metal gate in MOSFET.
  • Cobalt can also be used as a seed to enable plating of copper by electro-deposition.
  • Cobalt or a cobalt alloy can also be used as wiring instead of copper for one or more layers.
  • a capacitor (CAP) can be formed by successive layers of metal, insulator, metal (MIM) and a thin film resistor at the same level. Circuit designers can now wire to the TaN thin film resistor at the lowest metal level, which reduces parasitics and allows more efficient usage of the existing wiring levels.
  • the excess copper and/or cobalt and the adhesion / barrier layer comprising Co in form of, for example metal nitrides or metal carbon nitrides, such as Co/TaN, Co/TiN, Co/TaCN, Co/TiCN, or for example as a single cobalt alloy layer, such as CoMo, CoTa, CoTi and CoW above the dielectrics, can be removed by the chemical mechanical polishing process according to the invention.
  • this cobalt and/or cobalt alloy can be produced or obtained in different ways.
  • Cobalt or cobalt alloys can be produced by ALD, PVD or CVD processes. It is possible that cobalt or the cobalt alloy is deposited onto a barrier material. Proper materials for barrier application are well known in the arts.
  • the barrier prevents metal atoms or ions like cobalt or copper from dif- fusing into the dielectric layer and improves the adhesion properties of the conductive layer.
  • Ta/TaN, Ti/TiN can be used.
  • this cobalt and/or cobalt alloy can be of any type, form, or shape. This cobalt and/or cobalt alloy preferably has the shape of a layer and/or overgrowth.
  • the cobalt and/or cobalt alloy content is preferably more than 90%, more preferably more than 95%, most preferably more than 98%, partic- ularly more than 99%, for example more than 99.9% by weight of the corresponding layer and/or overgrowth.
  • This cobalt and/or cobalt alloy has been preferably filled or grown in trenches or plugs between other substrates, more preferably filled or grown in trenches or plugs in dielectric materials like for example S1O2, silicon, low-k (BD1 , BD2) or ultra low-k materials, or other isolating and semiconducting material used in the semiconductor industry.
  • the down pressure or down force is a downward pressure or a downward force which is applied by the carrier to the wafer pressing it against the pad during CMP.
  • This down pressure or down force can for example be measured in pound per square inch (abbreviated as psi)
  • the down pressure is 2 psi or lower.
  • the down pressure is in the range of from 0.1 to 1.9 psi, more preferably in the range of from 0.3 to 1 .8 psi, most preferably in the range of from 0.4 to 1 .7 psi, particularly preferable in the range of from 0.8 to 1 .6 psi, for example 1 .3 psi.
  • the selectivity of cobalt to copper with regard to the material removal rate is preferably higher than 0.05, more preferably higher than 0.2, most preferably higher than 1 , particularly higher than 2.5, especially higher than 20, for example higher than 40.
  • This selectivity profile can be adjusted for example by varying the concentration of hydrogen peroxide (D), the concentration of the corrosion inhibitor (C) and the concentration of the abrasive (A) of the CMP composition (Q).
  • the CMP composition (Q) used according to the invention is for chemical-mechanical polishing of a substrate used in the semiconductor industry comprising cobalt or cobalt and copper and / or of a cobalt alloy.
  • the cobalt and/or cobalt alloy can be of any type, form, or shape.
  • the cobalt and/or cobalt alloy preferably has the shape of a layer and/or overgrowth. If this cobalt and/or cobalt alloy has the shape of a layer and/or overgrowth, the cobalt and/or cobalt alloy content is preferably more than 90%, more preferably more than 95%, most preferably more than 98%, particularly more than 99%, for example more than 99.9% by weight of the corresponding layer and/or overgrowth.
  • the cobalt and/or cobalt alloy has been preferably filled or grown in trenches or plugs between other substrates, more preferably filled or grown in trenches or plugs in dielectric materials like for example S1O2, silicon, low-k (BD1 , BD2) or ultra low-k materials, or other isolating and semiconducting material used in the semiconductor industry.
  • dielectric materials like for example S1O2, silicon, low-k (BD1 , BD2) or ultra low-k materials, or other isolating and semiconducting material used in the semiconductor industry.
  • TSV Through Silicon Vias
  • photoresist and/or pol- yimide can be used as insulating material between the subsequent processing steps of wet etch and CMP for insulating/isolating properties after revealing the TSV from the backside of the wafer.
  • barrier materials to prevent metal ions from diffusing into the dielectric material can for example be Ti/TiN, Ta/TaN or Ru or Ru-alloys, Co or Co-alloys.
  • the selectivity of cobalt to copper with regard to the material removal rate is preferably higher than 0.05, more preferably higher than 0.2, most preferably higher than 1 , particularly higher than 2.5, especially higher than 20, for example higher than 40.
  • the selectivity may be advantageously be adjusted by the combination of high material removal rate (MRR) of cobalt and low MRR of copper or the other way round.
  • MRR material removal rate
  • At least one corrosion inhibitor in a total amount of from 0,008 to 0,02 wt.-% based on the total weight of the respective CMP composition
  • CMP composition (Q) has a pH in the range of from 7.1 to 9.
  • 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
  • A Fumed inorganic particles (A) 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
  • CMP composition (Q) has a pH in the range of from 6 to 9.5.
  • CMP composition (Q) has a pH in the range of from 6 to 9.5.
  • CMP composition (Q) has a pH in the range of from 6 to 9.
  • (B) is glycine, alanine, leucine, cysteine or a mixture or salt thereof in a total amount of from 0,45 to 0,82 wt.-% based on the total weight of the respective CMP composi tion (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
  • CMP composition (Q) has a pH in the range of from 6 to 9.5.
  • (B) is glycine, alanine, leucine, cysteine or a mixture or salt thereof in a total amount of from 0,2 to 0,9 wt.-% based on the total weight of the respective CMP composition
  • CMP composition (Q) has a pH in the range of from 6 to 9.5.
  • (B) is glycine, alanine, leucine, cysteine in a total amount of from 0,2 to 0,9 wt.-%
  • (C) is 5 methyl-benzotriazole, 1 ,2,4 triazole, 1 H-benzotriazole, benzotriazole or a mix ture thereof in a total amount of from 0,007 to 0,018 wt.-% based on the total weight of the respective CMP composition
  • CMP composition (Q) has a pH in the range of from 6 to 9.5.
  • At least one corrosion inhibitor in a total amount of from 0,008 to 0,02 wt.-% based on the total weight of the respective CMP composition
  • CMP composition (Q) has a pH in the range of from 7.1 to 9.
  • Processes for preparing CMP compositions are generally known. These processes may be applied to the preparation of the CMP composition of the invention. This can be carried out by dispersing or dissolving the above-described components (A), (B), (C), (D) and optional components (F) to (H) in the aqueous medium (E), preferably water, and optionally by adjusting the pH value through adding an acid, a base, a buffer or a pH adjusting agent.
  • the customary and standard mixing processes and mixing apparatuses such as agitated vessels, high shear impellers, ultrasonic mixers, homogenizer nozzles or counterflow mixers, can be used.
  • the polishing process is generally known and can be carried out with the processes and the equipment under the conditions customarily used for the CMP in the fabrication of wafers with integrated circuits. There is no restriction on the equipment with which the polishing process can be carried out.
  • typical equipment for the CMP process consists of a rotating platen which is covered with a polishing pad. Also orbital polishers have been used.
  • the wafer is mounted on a carrier or chuck.
  • the side of the wafer being processed is facing the polishing pad (single side polishing process).
  • a retaining ring secures the wafer in the horizontal position.
  • the larger diameter platen is also generally horizontally positioned and presents a surface parallel to that of the wafer to be polished.
  • the polishing pad on the platen con- tacts the wafer surface during the planarization process.
  • the wafer is pressed onto the polishing pad.
  • Both the carrier and the platen are usually caused to rotate around their respective shafts extending perpendicular from the carrier and the 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, though not necessarily, the same as that of the platen.
  • the speeds of rotation for the carrier and the platen are generally, though not necessarily, set at different values.
  • Dur- ing the CMP process of the invention the CMP composition of the invention is usually applied onto the polishing pad as a continuous stream or in dropwise fashion. Customarily, the temperature of the platen is set at temperatures of from 10 to 70°C.
  • the load on the wafer can be applied by a flat plate made of steel for example, covered with a soft pad that is often called backing film. If more advanced equipment is being used a flexible membrane that is loaded with air or nitrogen pressure presses the wafer onto the pad. Such a membrane carrier is preferred for low down force processes when a hard polishing pad is used, because the down pressure distribution on the wafer is more uniform compared to that of a car- rier with a hard platen design. Carriers with the option to control the pressure distribution on the wafer may also be used according to the invention. They are usually designed with a number of different chambers that can be loaded to a certain degree independently from each other.
  • wafers with integrated circuits comprising a surface region containing or consisting of cobalt or cobalt and copper and / or of a cobalt alloy can be obtained which have an excellent functionali- ty.
  • the CMP composition of the invention can be used in the CMP process as ready-to-use slurry, they have a long shelf-life and show a stable particle size distribution over long time. Thus, they are easy to handle and to store. They show an excellent polishing performance, particularly a controllable and adjustable selectivity between cobalt and copper by the combination of high material removal rate (MRR) of cobalt and low MRR of copper or the other way round. Since the amounts of its components are held down to a minimum, the CMP composition according to the invention respectively can be used in a cost-effective way.
  • MRR material removal rate
  • Figure 1 Schematic illustration of the variation of the shape factor with the shape of a particle
  • Figure 2 Schematic illustration of the variation of the sphericity with the elongation of a particle
  • FIG. 3 Schematic illustration of the Equivalent Circle Diameter (ECD)
  • FIG. 4 Energy Filtered-Transmission Electron Microscopy (EF-TEM) (120 kilo volts) image of a dried cocoon-shaped silica particle dispersion with 20 wt.% solid content on a carbon foil
  • Figure 6 Cu material removal rate in dependency of the H2O2 concentration at low particles concentration of 0.5 wt.% (A) and at high particles concentration of 4.9 wt.% (A).
  • Figure 7 Dependency of the Co and Cu material removal rate from the down pressure at 1 wt. % H2O2 concentration.
  • backing film Strasbaugh, DF200 (136 holes);
  • conditioning tool Strasbaugh, soft brush, ex-situ; after each wafer the pad is conditioned for the next processing of an other wafer by 2 sweeps with 5lbs down force.
  • the brush is soft. This means even after 200 sweeps the brush will not have caused a significant removal rate on the soft polishing pad.
  • Three dummy TEOS wafers are polished with 60s before the metal wafers are polished (Co wafer is polished for 15 s, Cu for 60 s).
  • the slurry is stirred in the local supply station.
  • Removal rate is determined by difference of weight of the wafers pre and post CMP by a Sarto- rius LA310 S scale or a NAPSON 4-point probe station.
  • the radial unifomity of removal rate is assessed by 39 point diameter scan (range) using NAP- SON 4-point probe station.
  • Low k material black diamond 1 st generation (referred to as "BD1 " in the following);
  • the pH - value is measured with a pH combination electrode (Schott, blue line 22 pH electrode).
  • Standard procedure for slurry preparation An aqueous solution of glycine 4.2 wt.% is prepared by dissolving the desired amount of glycine in ultra-pure water. After stirring for 20 min the solution is neutralized and the pH is adjusted to pH 8.05 ⁇ 0.1 by adding an 4.8 wt.% aqueous solution of KOH. Balance water may be added to adjust concentration.
  • An aqueous solution of BTA 0.34 wt.% is prepared by dissolving the desired amount of BTA in ultra-pure water and stirring for 30 minutes until all of the solid BTA is dissolved.
  • the 1 wt.% non-ionic surfactant stock solution is prepared by dissolving the desired amount of surfactant (F) (for example TritonTM DF 16 from Dow) in ultra-pure water by stirring for 30 minutes.
  • F surfactant
  • the glycine (amino acid (B)) solution, the BTA (corrosion inhibitor (C)) solution and the surfactant (F) solution are mixed and a solution of colloidal silica particles (30 % stock solution of (A) for example Fuso ® PL 3) is added under continuous stirring.
  • a solution of colloidal silica particles (30 % stock solution of (A) for example Fuso ® PL 3) is added under continuous stirring.
  • the pH is adjusted to 8.3 ⁇ 0.1 by adding an 4.8 wt.% aqueous solution of KOH.
  • Balance water is added under stirring to adjust the concentration of the CMP slurry to the values listed in the tables 2, 3, 4 and 5 of the examples and comparative examples below.
  • the dispersion is filtered by passing through a 0.2 ⁇ filter at room temperature.
  • the desired amount of H2O2 (D) is added right before (1 to 15 min) before the slurry is used for CMP.
  • the slurries for the examples Comp. Ex V3. V4, V5 and V6 were prepared according to a modi- fied version of the standard slurry preparation procedure.
  • a slurry according to standard procedure was prepared but without BTA (C).
  • BTA (C) was added (1 % stock solution) subsequently under stirring.
  • the desired amount of H2O2 (D) is added right before (1 to 15 min) the slurry is used for CMP.
  • the slurries for the examples Comp. Ex V7 to V15 were prepared with a modified version of the standard slurry preparation procedure.
  • Colloidal cocoon-shaped Silica particles having an average primary particle size (d1 ) of 35 nm and an average secondary particle size (d2) of 70 nm (as determined using dynamic light scat- tering techniques via a Horiba instrument) (for example Fuso ® PL-3) were used.
  • aqueous cocoon-shaped silica particle dispersion with 20 wt.% solid content was dispersed on a carbon foil and was dried.
  • the dried dispersion was analyzed by using Energy Filtered- Transmission Electron Microscopy (EF-TEM) (120 kilo volts) and Scanning Electron Microscopy secondary electron image (SEM-SE) (5 kilo volts).
  • EF-TEM Energy Filtered- Transmission Electron Microscopy
  • SEM-SE Scanning Electron Microscopy secondary electron image
  • the EF-TEM image with a resolution of 2k, 16 Bit, 0.6851 nm/pixel (figure 4) was used for the analysis.
  • the images were binary coded using the threshold after noise suppression. Afterwards the particles were manually separated. Overlying and edge particles were discriminated and not used for the analysis.
  • ECD, shape factor and sphericity as defined before were calculated and statistically classified.
  • surfactant (F) an amphiphilic non-ionic polyoxyethylene-polyoxypropylene alkyl ether surfactant is used, which is a mixture of molecules containing, on the average, an alkyl group having 6 to 12 carbon atoms and 2 to 10 oxyethylene monomer units and 1 to 5 oxypro- pylene monomer units in random distribution (for example TritonTM DF 16 from DOW).
  • E ultra-pure water
  • BD1 black diamond 1 st generation
  • the material removal rate is strongly dependent from the H2O2 concentration.
  • 3 types of regions can be defined in dependency of the H2O2 concentration.
  • the copper removal rate is very low and not influenced by an increase in the H2O2 concentration.
  • the copper removal rate increases.
  • the copper removal rate is independent from an increase of the H2O2 concentration.
  • the cobalt removal rate increases already with very low H2O2 concentrations of at least 0.05 wt.%.
  • the cobalt removal rate reaches a maximum at 0.4 wt.% H2O2 and then de- creases. Based on this surprisingly found dependency the selectivity of cobalt to copper can be easily adjusted by varying the H2O2 concentration.
  • the variation of the corrosion inhibitor concentration (C) shows a strong effect on the cobalt and copper material removal rate.
  • the copper removal rate increases in a linear way by increasing the down pressure.
  • a linear increase of down pressure leads to an exponential increase of the cobalt material removal rate (see figure 7).
  • the low down pressure regime according to the invention is favorable.
  • the CMP compositions of the examples 1 to 12 according to the invention are showing improved performance, in terms of cobalt to copper selectivity, high material removal rates of cobalt at low abrasive (A) concentration, low material removal rates of the low k material, for ex- ample black diamond 1 st generation (BD1 ), a low etching behavior and a high dispersion stability.
  • the selectivity can be increased by up to a factor of 41 by using CMP compositions according to the invention.
  • the selectivity can be adjusted within a wide range.

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Abstract

L'invention concerne une composition de polissage mécano-chimique (CMP) (Q) comprenant (A) des particules colloïdales ou des particules inorganiques sublimées (A) ou un mélange de ces dernières dans une quantité totale de 0,0001 à 2,5 % en poids par rapport au poids total de la composition de CMP respective ; (B) au moins un acide aminé dans une quantité totale de 0,2 à 1 % en poids par rapport au poids total de la composition de CMP respective ; (C) au moins un inhibiteur de corrosion dans une quantité totale de 0,001 à 0,02 % en poids par rapport au poids total de la composition de CMP respective ; (D) du peroxyde d'hydrogène comme agent oxydant dans une quantité totale de 0,0001 à 2 % en poids par rapport à la quantité totale de la composition de CMP respective ; (E) un milieu aqueux ; la composition de CMP (Q) ayant un pH compris entre 6 et 9,5.
PCT/EP2015/066086 2014-07-15 2015-07-14 Composition de polissage mécano-chimique (cmp) WO2016008896A1 (fr)

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EP15736840.8A EP3169737B1 (fr) 2014-07-15 2015-07-14 Composition pour polissage mécanique chimique
JP2017502617A JP6817186B6 (ja) 2014-07-15 2015-07-14 化学機械研磨（ｃｍｐ）組成物
CN201580037575.3A CN106661382B (zh) 2014-07-15 2015-07-14 化学机械抛光(cmp)组合物
KR1020177003150A KR102501836B1 (ko) 2014-07-15 2015-07-14 화학 기계적 연마 (cmp) 조성물
SG11201700255UA SG11201700255UA (en) 2014-07-15 2015-07-14 A chemical mechanical polishing (cmp) composition
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TWI737697B (zh) * 2016-03-22 2021-09-01 德商巴斯夫歐洲公司 化學機械研磨（cmp）組成物用於研磨含鈷及/或鈷合金之基板的用途，化學機械研磨（cmp）組成物，及製造半導體裝置之方法
CN109153886B (zh) * 2016-04-27 2021-12-21 巴斯夫欧洲公司 化学机械抛光(cmp)组合物在抛光包含钴和/或钴合金的基材中的用途
IL262380B (en) * 2016-04-27 2022-08-01 Basf Se Use of chemical mechanical polishing preparation for polishing substrates containing cobalt and/or cobalt alloy
CN109153886A (zh) * 2016-04-27 2019-01-04 巴斯夫欧洲公司 化学机械抛光(cmp)组合物在抛光包含钴和/或钴合金的基材中的用途
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US11264250B2 (en) 2016-04-27 2022-03-01 Basf Se Use of a chemical mechanical polishing (CMP) composition for polishing of cobalt and / or cobalt alloy comprising substrates
US10077382B1 (en) 2017-03-06 2018-09-18 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Method for polishing cobalt-containing substrate
US10233356B2 (en) 2017-03-06 2019-03-19 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Polishing slurry for cobalt-containing substrate
US10377921B2 (en) 2017-09-21 2019-08-13 Rohm and Haas Electronics Materials CMP Holdings, Inc. Chemical mechanical polishing method for cobalt
US10170335B1 (en) 2017-09-21 2019-01-01 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Chemical mechanical polishing method for cobalt
CN113278366A (zh) * 2019-12-31 2021-08-20 清华大学 一种基板的铜互连钴阻挡层

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