Polycationic polymers or copolymers with different cationic types for slurries for chemical mechanical planarization

Abstract

Synthesis of polycationic polymers or copolymers is disclosed. The polycationic polymer or copolymer is formed from at least one first cationic monomer and at least one second cationic monomer, wherein the first cationic monomer and the second cationic monomer have different cationic groups; such as imidazolium groups and non-imidazolium groups. Also disclosed is a chemical mechanical planarization (CMP) slurry comprising an abrasive; an activator; an oxidant; an additive comprising a polycationic polymer or copolymer; and water. The use of synthetic polycationic polymers or copolymers in CMP slurries reduces sagging and erosion in high selectivity tungsten slurries.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 362,810, filed on April 11, 2022, the entire contents of which are incorporated herein by reference for all permitted purposes. Background Art

[0003] The present disclosure relates to chemical mechanical planarization or polishing ("CMP") slurries (or compositions or formulations), polishing methods, and polishing systems for chemical mechanical planarization in the production of semiconductor devices. In particular, the present disclosure relates to polishing slurries suitable for polishing patterned semiconductor wafers including tungsten-containing metal materials.

[0004] Chemical mechanical polishing or planarization (CMP) has been successfully used in the manufacturing process of integrated circuits for decades. It is considered a key and enabling technology for the demand for miniaturization.

[0005] Integrated circuits are interconnected using well-known multi-layer interconnects. The interconnect structure typically has a first metallization layer, an interconnect layer, a second metallization layer, and typically a third and subsequent metallization layers. Interlayer dielectric materials such as silicon dioxide and sometimes low-k materials are used to electrically isolate different metallization layers in a silicon substrate or well. Electrical connections between different interconnect layers are achieved by using metallized vias, particularly tungsten vias. U.S. Patent No. 4,789,648 describes a method for preparing multiple metallization layers and metallized vias in an insulating film. In a similar manner, metal contacts are used to form electrical connections between devices formed in the interconnect layers and wells. The metal vias and contacts are typically filled with tungsten, and an adhesion layer such as titanium nitride (TiN) and / or titanium is typically used to adhere the metal layer (such as a tungsten metal layer) to the dielectric material.

[0006] In one semiconductor manufacturing process, metallized vias or contacts are formed by blanket tungsten deposition followed by a CMP step. In a typical process, vias are etched through the interlayer dielectric (ILD) to the interconnect or semiconductor substrate. Next, a thin adhesion layer such as titanium nitride and / or titanium is typically formed on the ILD and directed into the etched via. Then, a tungsten film is blanket deposited over the adhesion layer and into the via. Deposition continues until the via is filled with tungsten. Finally, excess tungsten is removed by CMP to form a metal via.

[0007] In another semiconductor manufacturing process, tungsten is used as a gate electrode material in transistors because its electrical properties are superior to polysilicon, which is traditionally used as a gate electrode material, as taught in A. Yagishita et al., IEEE TRANSACTIONS ONELECTRON DEVICES, Vol. 47, No. 5, May 2000.

[0008] In a typical CMP process, the substrate is brought into direct contact with a rotating polishing pad. The carrier applies pressure to the back side of the substrate. During polishing, the polishing pad and platen rotate while maintaining a downward force on the back side of the substrate. During polishing, an abrasive and chemically reactive solution, often referred to as a polishing "slurry", a polishing "composition" or a polishing "formulation", is deposited onto the pad, wherein the rotation and / or movement of the pad relative to the wafer brings the slurry into the space between the polishing pad and the substrate surface. The slurry initiates the polishing process by chemically reacting with the film being polished. As the slurry is provided to the wafer / polishing pad interface, the polishing process is facilitated by the rotational motion of the pad relative to the substrate. Polishing continues in this manner until the desired film on the insulator is removed. The removal of tungsten in CMP is believed to be due to the synergistic effect between mechanical wear and tungsten oxidation and subsequent dissolution.

[0009] Despite its relatively simple outward appearance, chemical mechanical planarization (CMP) is a highly complex process, as described by Lee Cook in Digital Encyclopedia of Applied Physics, 2019, DOI: 10.1002 / 3527600434.eap847 10.1002 / 3527600434.eap847; and most of the time, CMP technology evolves faster than Seo, J describes based on his understanding in Journal of materials research 2021, 36(1), 235.1.

[0010] Its importance as a technology to achieve past and future device scaling requirements and new trends in the semiconductor industry is indisputable. A large number of interactions between wafers, slurries and pads, as well as general process parameters, determine the results of CMP. Ultimately, material removal in CMP is the result of a complex interaction between chemical and mechanical forces, as described in Lee, D.; Lee, H.; Jeong, H., Slurry components in metal chemical mechanical planarization (CMP) process: A review. International Journal of Precision Engineering and Manufacturing 2016, 17, 1751. A large number of materials are used in semiconductor device manufacturing, all of which require optimized CMP processes. Simultaneous polishing of a combination of completely different materials, such as dielectric materials, barrier layers, and metal layers, is a real challenge for CMP.

[0011] One of the problems commonly encountered in CMP, especially in metal applications such as tungsten, is how to control topological defects such as erosion and dishing. Smaller feature sizes and devices at the 7nm node and above impose even more stringent requirements on acceptable defect levels during polishing.

[0012] Highly selective slurries (which have a large difference between metal removal rates and dielectric removal rates) are of great significance for future industry needs. However, there are also drawbacks associated with the use of these highly selective slurries. The metal layer can easily be over-polished, resulting in a "dimpling" effect. Another unacceptable defect is called "erosion", which describes the difference in topography between areas with dielectrics and dense arrays of metal vias or trenches.

[0013] Specially designed water-based slurries are considered to be the main driving force for improving CMP performance for future devices. Slurry development not only affects the removal rate and selectivity between different layers, but also controls defects during the polishing process. In general, slurry compositions are complex combinations of abrasives and chemical components with different functions. As dispersants, passivators or generally as topography control additives, polymer additives play a key role in slurry development to obtain the desired removal rate, selectivity and minimize surface defects by interacting with certain materials. For example, positively charged polymers inhibit tungsten removal and can be used to reduce the dishing effect during tungsten CMP.

[0014] US 5,876,490 describes the use of a polishing slurry comprising abrasive particles and exhibiting a normal stress effect, and further comprising a polyelectrolyte having an ionic portion having a charge different from the charge associated with the abrasive particles, wherein the concentration of the polyelectrolyte is from about 5 to about 50 weight percent of the abrasive particles, and wherein the molecular weight of the polyelectrolyte is from about 500 to about 10,000.

[0015] US2010 / 0075501A1 describes a chemical mechanical polishing aqueous dispersion for polishing a polishing target including an interconnect layer containing tungsten. The chemical mechanical polishing aqueous dispersion comprises: (A) a cationic water-soluble polymer; (B) an iron (III) compound; and (C) colloidal silica particles. The content (M) of the cationic water-soluble polymer (A) is A ) (mass %) and the content of the iron (III) compound (B) (M B )(mass %) satisfies the relationship “M A / M B =0.004 to 0.1". The pH of the chemical mechanical polishing aqueous dispersion is 1 to 3.

[0016] US2010 / 0252774 A1 describes a chemical mechanical polishing aqueous dispersion for polishing a polishing target including a wiring layer containing tungsten. The chemical mechanical polishing aqueous dispersion comprises: (A) a cationic water-soluble polymer; (B) an iron (III) compound; and (C) colloidal silica having an average particle size of 10 to 60 nm calculated by the specific surface area measured by the BET method. The content (M) of the cationic water-soluble polymer (A) is A ) (mass %) and the content of colloidal silica (C) (M C )(mass %) satisfies the relationship “M A / M C =0.0001 to 0.003". The chemical mechanical polishing aqueous dispersion.

[0017] US10,604,678B1 discloses a method and composition for polishing tungsten, which contains a selected low concentration of a quaternary phosphonium compound to at least reduce the erosion rate of tungsten. The method and composition include providing a tungsten-containing substrate, providing a stable polishing composition, which contains as initial components: water, an oxidizing agent: a selected low concentration of a quaternary phosphonium compound to at least reduce the erosion rate: a dicarboxylic acid. A source of iron ions: a colloidal silica abrasive and optionally a pH adjuster; providing a chemical mechanical polishing pad having a polishing surface; generating dynamic contact at the interface between the polishing pad and the substrate; and dispensing the polishing composition onto the polishing surface at or near the interface between the polishing pad and the substrate; wherein some tungsten is polished off the substrate and the erosion rate of tungsten is reduced.

[0018] US 2009 / 0081871 A1 discloses a method comprising chemically mechanically polishing a substrate with an invented polishing composition comprising a liquid carrier, a cationic polymer, an acid, and abrasive particles that have been treated with an aminosilane compound.

[0019] US2014 / 0248823A1 describes a chemical-mechanical polishing composition comprising (a) abrasive particles, (b) a polymer, and (c) water, wherein (i) the polymer has an overall charge, (ii) the abrasive particles have a zeta potential Za measured in the absence of the polymer, and the abrasive particles have a zeta potential Zb measured in the presence of the polymer, wherein the zeta potential Za is a value with the same sign as the overall charge of the polymer, and (iii) the Izeta potential Z bI >Izeta potential Z aI The invention also provides a method for polishing a substrate using the polishing composition.

[0020] In U.S. Provisional Application Nos. 63 / 191,047, filed on May 20, 2021; 63 / 209,306, filed on June 10, 2021; and 63 / 251,127, filed on October 1, 2021, imidazolium-type cationic polymers, phosphonium-based polyionic liquids, and triazole- or triazolium-based polymers were identified and used in CMP slurries, respectively; which are incorporated herein by reference in their entirety.

[0021] One of the problems commonly encountered in CMP, especially in metal applications such as tungsten, is the dishing of tungsten lines and the erosion of the metal line array. Disk and erosion are key CMP parameters that define the planarity of the polished wafer. For wider lines, the dishing of the line generally increases. The erosion of the array generally increases with increasing density of metal lines in a given array of a patterned wafer.

[0022] Tungsten CMP slurries must be formulated so that dishing and erosion can be minimized to meet certain design goals that are critical to a functional device.

[0023] Finding solutions to control topographic defects such as erosion and dishing is key to future CMP needs. There remains a need for novel tungsten CMP slurries that can reduce dishing and erosion while maintaining a desired removal rate during polishing. Summary of the invention

[0024] The present invention meets the need by providing intelligently designed tungsten CMP slurries, systems, and methods of using the same to minimize the described dishing and erosion problems in highly selective tungsten slurries while maintaining the desired polishing of metal layers, particularly tungsten films.

[0025] More specifically, the present invention discloses the synthesis of polycationic polymers or copolymers. The polycationic polymers or copolymers are formed from at least one first cationic monomer and at least one second cationic monomer, wherein the first cationic monomer and the second cationic monomer have different cationic groups; such as imidazolium groups and non-imidazolium groups. CMP slurries using polycationic polymers have been shown to reduce the described problems; namely, dishing and erosion.

[0026] The polycationic polymer or copolymer has at least one first cationic monomer having at least one imidazolium group and at least one second cationic monomer having at least one cationic group that is not imidazolium.

[0027] Furthermore, several specific aspects of the invention are summarized below.

[0028] Aspect 1: A polycationic polymer or copolymer formed from at least one first cationic monomer and at least one second cationic monomer;

[0029] in

[0030] The at least one first cationic monomer comprises the structure of (I):

[0031]

[0032] in:

[0033] P 1 represents a polymerizable group;

[0034] Sp 1 represents a spacer group or a single bond, and may be selected from linear, branched and cyclic alkyl groups; wherein CH 2 may be replaced by O, S or N in such a way that no heteroatoms are attached to each other, and hydrogen may be replaced by F, Cl or CN;

[0035] R 1 , R 2 , R 3 are each independently H, or a substituted or unsubstituted aliphatic, aromatic, heteroaromatic or siloxane moiety, wherein CH 2 may be replaced by O, S or N in such a way that no heteroatoms are attached to one another; and wherein hydrogen may be replaced by F, Cl or CN;

[0036] R 4 is a substituted or unsubstituted straight chain, cyclic or branched aliphatic group;

[0037] X - represents anionic counter ions;

[0038] as well as

[0039] The at least one second cationic monomer comprises the structure of (II):

[0040]

[0041] in:

[0042] P 2 represents a polymerizable group;

[0043] Sp 2 represents a spacer group or a single bond at each occurrence and may be selected from linear, branched and cyclic alkyl groups; wherein CH 2 may be replaced by O, S or N in such a way that no heteroatoms are attached to each other, and hydrogen may be replaced by F, Cl or CN;

[0044] R 1 , R 2 , R 3 is a substituted or unsubstituted aliphatic, cycloaliphatic or branched aliphatic, aromatic or heteroaromatic (CH 2may be replaced by O, S or N in a manner that no heteroatoms are attached to each other; hydrogen may be replaced by F, Cl or CN); and

[0045] X - represents anionic counter ions.

[0046] Aspect 2: A polycationic polymer or copolymer according to aspect 1, wherein the polymerizable group P 1 and P 2 At least one of the groups is selected from groups containing a C=C double bond.

[0047] Aspect 3: The polycationic polymer or copolymer according to aspects 1 to 2, wherein the anionic counterions in (I) and (II) may be the same or different and are each selected from halides (F-, Cl-, Br-, I-), BF 4 -PF 6 -, carboxylate, malonate, citrate, carbonate, fumarate, MeOSO 3 -MeSO 3 -、CF 3 COO-, CF 3 SO 3 -, nitrate and sulfate.

[0048] Aspect 4: The polycationic polymer or copolymer according to aspect 1, wherein the at least one first cationic monomer comprises 5 A cross-linkable structure, where R 5 Selected from formula (a):

[0049] -SP 3 -P 3

[0050] (a)

[0051] in:

[0052] Sp 3 represents a spacer group or a single bond at each occurrence and may be selected from linear, branched and cyclic alkyl groups; wherein CH 2 may be replaced by O, S or N in such a way that no heteroatoms are attached to each other, and hydrogen may be replaced by F, Cl or CN;

[0053] P 3 To be able to 1 The same or different polymerizable groups.

[0054] Aspect 5: A polycationic polymer or copolymer comprising at least one repeating unit of (A) and at least one repeating unit of (B):

[0055]

[0056] in:

[0057] L, at each occurrence, represents a spacer group or a single bond;

[0058] R 1 , R 2 and R 3 Each is independently H or a substituted or unsubstituted aliphatic, aromatic, heteroaromatic or siloxane moiety;

[0059] n is an integer from 1 to 500; and

[0060] X - represents anionic counter ions;

[0061]

[0062] in

[0063] L, at each occurrence, represents a spacer group or a single bond;

[0064] R 1 , R 2 Each is a substituted or unsubstituted aliphatic, aromatic, or heteroaromatic moiety;

[0065] m is an integer from 1 to 500; and

[0066] X - represents anionic counter ions.

[0067] Aspect 6: The polycationic polymer or copolymer according to aspect 5, wherein the spacer group L is selected from substituted or unsubstituted linear, cyclic or branched aliphatic groups; wherein CH 2 may be replaced by O, S or N in such a way that no heteroatoms are attached to one another, and wherein hydrogen may be replaced by F, Cl or CN.

[0068] Aspect 7: A polycationic polymer or copolymer according to aspects 1-6; wherein the polycationic polymer or copolymer is formed by a polymerization method selected from the following: free radical polymerization, reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP), atom transfer reaction polymerization (ATRP), ring-opening polymerization (ROMP) and condensation reaction.

[0069] Aspect 8: A chemical mechanical planarization composition comprising the polycationic polymer or copolymer according to aspects 1-7.

[0070] Aspect 9: A chemical mechanical planarization composition comprising:

[0071] an abrasive selected from the group consisting of inorganic oxide particles, inorganic oxide particles coated with metal oxides, organic polymer particles, organic polymer particles coated with metal oxides, and combinations thereof;

[0072] Activator;

[0073] Oxidants;

[0074] The polycationic polymer or copolymer according to aspects 1 to 7;

[0075] water; and optionally

[0076] Corrosion inhibitors;

[0077] Sag reducers;

[0078] Stabilizers;

[0079] pH adjuster.

[0080] Aspect 10: A system for chemical mechanical planarization, comprising:

[0081] a semiconductor substrate comprising at least one tungsten-containing surface;

[0082] Polishing pads; and

[0083] The chemical mechanical planarization composition according to aspects 8-9;

[0084] Wherein the at least one tungsten-containing surface is in contact with a polishing pad and a chemical mechanical planarization composition.

[0085] Aspect 11: A polishing method for chemical mechanical planarization of a semiconductor substrate comprising at least one tungsten-containing surface, comprising the steps of:

[0086] a) contacting at least one tungsten-containing surface with a polishing pad;

[0087] b) delivering a chemical mechanical planarization composition according to aspects 8-9;

[0088] c) polishing the at least one tungsten-containing surface with a chemical mechanical planarization composition.

[0089] Abrasives include, but are not limited to, inorganic oxide particles, metal oxide-coated inorganic oxide particles, organic polymer particles, metal oxide-coated organic polymer particles, and combinations thereof.

[0090] Inorganic oxide particles include, but are not limited to, ceria, colloidal silica, high purity colloidal silica, fumed silica, colloidal ceria, alumina, titania, and zirconia particles.

[0091] Metal oxide coated inorganic oxide particles include, but are not limited to, ceria coated inorganic oxide particles, such as ceria coated colloidal silica, ceria coated high purity colloidal silica, ceria coated alumina, ceria coated titania, ceria coated zirconia, or any other ceria coated inorganic oxide particles.

[0092] Organic polymer particles include, but are not limited to, polystyrene particles, polyurethane particles, polyacrylate particles, or any other organic polymer particles.

[0093] The metal oxide coated organic polymer particles are selected from the group consisting of ceria coated organic polymer particles and zirconium oxide coated organic polymer particles.

[0094] The concentration of the abrasive can be in the range of 0.01 wt % to 30 wt %, preferably about 0.05 wt % to about 20 wt %, more preferably about 0.01 to about 10 wt %, and most preferably 0.1 wt % to 2 wt %. The weight percentages are relative to the composition.

[0095] The activator includes, but is not limited to (1) inorganic oxide particles coated with a transition metal on the surface thereof; and the transition metal is selected from Fe, Cu, Mn, Co, Ce and combinations thereof; (2) a soluble catalyst selected from iron (III) nitrate, ammonium iron (III) oxalate trihydrate, iron (III) citrate monohydrate, iron (III) acetylacetonate and ethylenediaminetetraacetic acid, iron (III) sodium salt hydrate; (3) a metal compound with multiple oxidation states selected from Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V; and combinations thereof.

[0096] The activator ranges from 0.00001 wt % to 5.0 wt %, 0.0001 wt % to 2.0 wt %, 0.0005 wt % to 1.0 wt %, or 0.001 wt % to 0.5 wt %.

[0097] Oxidants include, but are not limited to, peroxy compounds selected from hydrogen peroxide, urea peroxide, peroxyformic acid, peroxyacetic acid, peroxypropionic acid, substituted or unsubstituted peroxybutyric acid, hydroperoxide-acetaldehyde, potassium periodate, ammonium peroxymonosulfate; and peroxy compounds selected from ferrous nitrite, KClO 4 , KBrO 4 、KMnO 4 Non-peroxide compounds.

[0098] The oxidant concentration may range from about 0.01 wt % to 30 wt %, with a preferred concentration of the oxidant being about 0.1 wt % to 20 wt %, and a more preferred concentration of the oxidant being about 0.5 wt % to about 10 wt %. The weight percentages are relative to the composition.

[0099] Typical amounts of additives comprising cationic polymers or copolymers range from 0.00001 wt% to 1 wt%, 0.0001 wt% to 0.5 wt%, 0.0005 wt% to 0.1 wt%, or 0.001 wt% to 0.06 wt%.

[0100] Suitable pH adjusters for lowering the pH of the polishing composition include, but are not limited to, nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids, and mixtures thereof. Suitable pH adjusters for increasing the pH of the polishing composition include, but are not limited to, potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and mixtures thereof.

[0101] The pH of the slurry is between 1 and 14, preferably between 1 and 7, more preferably between 1 and 6, and most preferably between 1.5 and 4.

[0102] The CMP slurry may further comprise a surfactant; a dispersant; a chelating agent; a film-forming anticorrosive agent; and a biocide.

[0103] Other aspects, features and embodiments of the invention will be more fully apparent from the ensuing disclosure and appended claims.

[0104] The embodiments of the present invention may be used alone or in combination with each other. DETAILED DESCRIPTION

[0105] The present invention meets the need by providing intelligently designed tungsten CMP slurries, systems, and methods of using the same to reduce the described problems of dishing and erosion in highly selective slurries while maintaining the desired polishing of metal layers, particularly tungsten films.

[0106] The present invention extends the general application range of cationic polymers to polycationic polymers or copolymers. Surprisingly, the combination of different cation types in one polycationic polymer or copolymer shows significantly better erosion and recession inhibition than the corresponding homopolymer alone.

[0107] Among the polymers for CMP slurries, the disclosed polycationic polymers or copolymers are surprisingly not described as additives for use in CMP slurries.

[0108] The present invention discloses the synthesis of polycationic polymers or copolymers; and demonstrates the use of the synthesized polycationic polymers or copolymers in CMP slurries to reduce the dishing and erosion problems described in highly selective tungsten slurries.

[0109] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0110] In the context of describing the present invention (especially in the context of the appended claims), the use of the terms "one" and "the" and similar indicators should be interpreted as covering the singular and plural, unless otherwise specified herein or clearly contradicted by the context. Unless otherwise specified, the terms "comprising", "having", "including" and "containing" should be interpreted as open terms (i.e., meaning "including, but not limited to"). Unless otherwise specified herein, the description of the numerical range herein is intended only to be used as a shorthand method for individually referring to each individual value falling within the range, and each individual value is incorporated into the specification as if it is individually described herein. Unless otherwise specified herein or clearly contradicted by the context, all methods described herein can be performed in any suitable order. The use of any and all examples or exemplary language (e.g., "such as") provided herein is only to better illustrate the present invention, rather than to limit the scope of the present invention, unless otherwise stated. Any language in the specification should not be interpreted as indicating that any unclaimed element is essential to the implementation of the present invention. Use of the term "comprising" in the specification and claims includes the narrower terms "consisting essentially of" and "consisting of.

[0111] Embodiments are described herein, including the best mode known to the inventor for implementing the present invention. After reading the foregoing description, changes in those embodiments may become apparent to those of ordinary skill in the art. The inventor expects that a skilled person will appropriately adopt these changes, and the inventor intends to implement the present invention in a manner different from that specifically described herein. Therefore, the present invention includes all modifications and equivalents of the subject matter described in the appended claims as allowed by applicable law. In addition, the present invention encompasses any combination of the above-mentioned elements in all possible variations, unless otherwise stated herein or clearly contradictory to the context.

[0112] For ease of reference, "microelectronic devices" correspond to semiconductor substrates, flat panel displays, phase change memory devices, solar panels and other products, including solar substrates, photovoltaic devices and micro-electromechanical systems (MEMS), which are manufactured for microelectronics, integrated circuits or computer chip applications. Solar substrates include, but are not limited to silicon, amorphous silicon, polycrystalline silicon, single crystal silicon, CdTe, copper indium selenide, copper indium sulfide and gallium arsenide on gallium. Solar substrates can be doped or undoped. It should be understood that the term "microelectronic device" is not meant to be limiting in any way, but includes any substrate that will eventually become a microelectronic device or microelectronic component.

[0113] "Substantially free" is defined herein as less than 0.001% by weight. "Substantially free" also includes 0.000% by weight. The term "free" means 0.000% by weight.

[0114] As used herein, "about" is intended to correspond to ±5%, preferably ±2% of the stated value.

[0115] In all such compositions where specific components of the composition are discussed with reference to weight percent ranges that include a lower limit of zero, it is understood that such components may or may not be present in various embodiments of the composition, and where such components are present, they may be present in concentrations as low as 0.00001 weight percent based on the total weight of the composition in which such components are employed.

[0116] The CMP slurry of the present invention comprises a polycationic polymer or copolymer.

[0117] More specifically, the CMP slurry comprises an abrasive, a polycationic polymer or copolymer, an oxidant (i.e., an oxidant that is not a free radical generator), an activator or catalyst, an additive, and water; optionally, a corrosion inhibitor, a dishing reducer, a stabilizer, and a pH adjuster. The pH of the slurry is 1-14, preferably 1-7, more preferably 1-6, and most preferably 1.5-4.

[0118] The CMP slurry may further comprise a surfactant; a dispersant; a chelating agent; a film-forming anticorrosive agent; a biocide; and a polishing enhancer.

[0119] Abrasive

[0120] Abrasives used in CMP slurries include, but are not limited to, inorganic oxide particles, metal oxide-coated inorganic oxide particles, organic polymer particles, metal oxide-coated organic polymer particles, surface-modified abrasive particles, and combinations thereof.

[0121] The abrasive used in the CMP slurry can be activator-containing particles (ie, abrasive having an activator coating); or non-activator-containing particles.

[0122] Inorganic oxide particles include, but are not limited to, ceria, silica, alumina, titania, germania, spinel, oxides or nitrides of tungsten, zirconium oxide particles, or any of the above doped with one or more other minerals or elements, and any combination thereof. Oxide abrasives may be produced by any of a variety of techniques, including sol-gel, hydrothermal, hydrolysis, plasma, pyrolysis, aerogel, fuming and precipitation techniques, and any combination thereof.

[0123] The precipitated inorganic oxide particles can be obtained by known methods by reaction of metal salts and acids or other precipitants. Pyrogenic metal oxide and / or metalloid oxide particles are obtained by hydrolysis of suitable gasifiable raw materials in an oxygen / hydrogen flame. An example is pyrogenic silicon dioxide from silicon tetrachloride. Pyrogenic oxides of aluminum oxide, titanium oxide, zirconium oxide, silicon dioxide, cerium oxide, germanium oxide and vanadium oxide and chemical and physical mixtures thereof are suitable.

[0124] Metal oxide coated inorganic oxide particles include, but are not limited to, ceria coated or alumina coated inorganic oxide particles, such as ceria coated colloidal silica, alumina coated colloidal silica, ceria coated high purity colloidal silica, alumina coated high purity colloidal silica, ceria coated alumina, ceria coated titania, alumina coated titania, ceria coated zirconia, alumina coated zirconia, or any other ceria coated or alumina coated inorganic oxide particles.

[0125] The metal oxide coated organic polymer particles are selected from ceria coated organic polymer particles, zirconium oxide coated organic polymer particles.

[0126] Organic polymer particles include, but are not limited to, polystyrene particles, polyurethane particles, polyacrylate particles, or any other organic polymer particles.

[0127] Colloidal silica particles and high purity colloidal silica particles are preferred abrasive particles. The silica may be any of precipitated silica, fumed silica, fumed silica, pyrogenic silica, silica doped with one or more additives, or any other silica-based compound.

[0128] Colloidal silica particles and high-purity colloidal silica particles used as abrasives also include silica particles with surface chemically modified by chemical coupling reactions, which allow such silica particles to have different chemical functional groups on the surface and have positive or negative charges under different applied pH conditions in the CMP slurry. Examples of such surface chemically modified silica particles include, but are not limited to, SiO 2-R-NH 2 、-SiO-R-SO 3 H, -SiO-SO 3 M; wherein R can be, for example, (CH 2 ) n The group wherein n ranges from 1 to 12 and M can be, for example, sodium, potassium or ammonium.

[0129] In an alternative embodiment, the silica may be produced, for example, by a method selected from a sol-gel method, a hydrothermal method, a plasma method, a fuming method, a precipitation method, and any combination thereof.

[0130] Abrasives are generally in the form of abrasive grains of a material or a combination of different materials, usually a plurality of abrasive grains. Generally, suitable abrasive grains are more or less spherical, with an effective diameter of about 10 to 700 nanometers, about 20 to 500 nanometers or about 30 to 300 nanometers (nm), although the size of individual particles may be different. Abrasives in the form of cocoon-shaped, aggregated or agglomerated particles are preferably further processed to form individual abrasive grains.

[0131] The abrasive grains may be purified using suitable methods such as ion exchange to remove metallic impurities, which may help to improve colloidal stability. Alternatively, high purity abrasive grains are used.

[0132] Generally, the above-mentioned abrasives can be used alone or in combination with each other. It may be advantageous to combine two or more abrasive particles of different sizes or different types of abrasives to obtain excellent performance.

[0133] The concentration of the abrasive can be in the range of 0.01 wt % to 30 wt %. Preferably, it is about 0.05 wt % to about 20 wt %, more preferably, it is about 0.01 wt % to about 10 wt %, and most preferably, it is 0.1 wt % to 2 wt %. The weight percentage is relative to the composition.

[0134] additive

[0135] The CMP slurry of the present invention comprises an additive which is a polycationic polymer or copolymer.

[0136] Negatively charged polymers are generally able to electrostatically interact with oppositely charged surfaces, such as positively charged tungsten surfaces. Therefore, using optimized amounts and tailored polymers can greatly improve the selectivity between metal removal and oxide layer removal while reducing the dishing effect.

[0137] At low pH values ​​<2.5, SiO, a classic standard oxide material 2 The layer is by no means partially negatively charged. In other words, to block oxide attack while simultaneously recessing the metal, the polymer used requires a more tailored design that goes beyond a purely cationic approach.

[0138] Surprisingly, specifically designed polycationic polymers or copolymers composed of different cation types with different geometries show very low recession and erosion behavior. This class of unique polymers can be used as morphology control additives and are valuable tools for designing next generation slurries.

[0139] A polycationic polymer or copolymer formed from at least one first cationic monomer and at least one second cationic monomer; wherein

[0140] The at least one first cationic monomer comprises the structure of (I):

[0141]

[0142] in:

[0143] P 1 represents a polymerizable group;

[0144] Sp 1 represents a spacer group or a single bond, and may be selected from linear, branched and cyclic alkyl groups; wherein CH 2 may be replaced by O, S or N in such a way that no heteroatoms are attached to each other, and hydrogen may be replaced by F, Cl or CN;

[0145] R 1 , R 2 , R 3 are each independently H; or a substituted or unsubstituted aliphatic, aromatic, heteroaromatic or siloxane moiety, wherein CH 2 may be replaced by O, S or N in such a way that no heteroatoms are attached to one another; and wherein hydrogen may be replaced by F, Cl or CN;

[0146] R 4 is a substituted or unsubstituted straight chain, cyclic or branched aliphatic group;

[0147] X - represents anionic counter ions;

[0148] as well as

[0149] At least one second cationic monomer comprises the structure of (II):

[0150]

[0151] in:

[0152] P 2 represents a polymerizable group;

[0153] Sp 2represents a spacer group or a single bond at each occurrence and may be selected from linear, branched and cyclic alkyl groups; wherein CH 2 may be replaced by O, S or N in such a way that no heteroatoms are attached to each other, and hydrogen may be replaced by F, Cl or CN;

[0154] R 1 , R 2 , R 3 is a substituted or unsubstituted aliphatic, cycloaliphatic or branched aliphatic, aromatic or heteroaromatic (CH 2 may be replaced by O, S or N in a manner that no heteroatoms are attached to each other; hydrogen may be replaced by F, Cl or CN); and

[0155] X - represents anionic counter ions.

[0156] Polymerizable group P 1 and P 2 Selected from groups containing a C=C double bond.

[0157] The anionic counterions in (I) and (II) may be the same or different and are each selected from halogen (F-, Cl-, Br-, I-), BF 4 -PF 6 -, carboxylate, malonate, citrate, carbonate, fumarate, MeOSO 3 -MeSO 3 -、CF 3 COO-, CF 3 SO 3 -, nitrate and sulfate.

[0158] At least one first cationic monomer comprises R 4 A cross-linkable structure, where R 4 Selected from formula (a):

[0159] -SP 3 -P 3

[0160] (a)

[0161] in:

[0162] Sp 3 represents a spacer group or a single bond at each occurrence and may be selected from linear, branched and cyclic alkyl groups; wherein CH 2 may be replaced by O, S or N in such a way that no heteroatoms are attached to each other, and hydrogen may be replaced by F, Cl or CN;

[0163] P 3 To be able to 1 The same or different polymerizable groups.

[0164] The polycationic polymer or copolymer may have at least one repeating unit of (A) and at least one repeating unit of (B):

[0165]

[0166] in:

[0167] L, at each occurrence, represents a spacer group or a single bond;

[0168] R 1 , R 2 and R 3 Each is independently H or a substituted or unsubstituted aliphatic, aromatic, heteroaromatic or siloxane moiety;

[0169] n is an integer from 1 to 500; and

[0170] X - represents anionic counter ions;

[0171]

[0172] in

[0173] L, at each occurrence, represents a spacer group or a single bond;

[0174] R 1 , R 2 Each is a substituted or unsubstituted aliphatic, aromatic, or heteroaromatic moiety;

[0175] m is an integer from 1 to 500; and

[0176] X - represents anionic counter ions.

[0177] Wherein the spacer group L is selected from substituted or unsubstituted straight chain, cyclic or branched aliphatic groups; wherein CH 2 may be replaced by O, S or N in such a way that no heteroatoms are attached to one another, and wherein hydrogen may be replaced by F, Cl or CN.

[0178] The polycationic polymer or copolymer may be formed by a polymerization process selected from free radical polymerization, reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide mediated polymerization (NMP), atom transfer reaction polymerization (ATRP), ring opening polymerization (ROMP) and polycondensation.

[0179] Examples of polycationic polymers or copolymers include, but are not limited to, poly(vinyl-3-ethyl-1H-imidazol-3-ium-co-tributyl-(4-vinylbenzyl)-phosphonium) bromide chloride:

[0180]

[0181] The concentration of the additive ranges from about 0.00001 wt % to 1.0 wt %, about 0.0001 wt % to 0.5 wt %, about 0.00025 wt % to 0.1 wt %, or about 0.0005 wt % to 0.05 wt %.

[0182] Oxidants

[0183] The CMP slurry of the present invention contains an oxidizing agent or oxidizing agent for chemical etching of materials.

[0184] The oxidant of the CMP slurry is in the fluid composition that contacts the substrate and helps to chemically remove the target material on the substrate surface. Therefore, the oxidant component is considered to improve or increase the material removal rate of the composition. Preferably, the amount of oxidant in the composition is sufficient to assist the chemical removal process while minimizing handling, environmental or similar or related issues, such as cost, as low as possible.

[0185] Advantageously, in one embodiment of the invention, the oxidant is a component that generates free radicals when exposed to at least one activator, thereby generating an increased etch rate on at least a selected structure. The free radicals described below oxidize most metals and make the surface more susceptible to oxidation by other oxidants. However, the oxidants are listed separately from the "free radical generating compounds" discussed below because some oxidants do not readily form free radicals when exposed to an activator, and in some embodiments, it is advantageous to have one or more oxidants that provide matched etching or preferential etching rates on various metal combinations that may be present on the substrate.

[0186] As is known in the art, some oxidants are better suited for certain components than for other components. In some embodiments of the invention, the selectivity of the CMP system for one metal relative to another is maximized, as is known in the art. However, in certain embodiments of the invention, the combination of oxidants is selected to provide substantially similar CMP rates (as opposed to simple etch rates) for the conductor and barrier layer combination.

[0187] In one embodiment, the oxidizing agent is an inorganic or organic per-compound.

[0188] Percompounds are generally defined as compounds containing an element in its highest oxidation state, such as perchloric acid, or compounds containing at least one peroxide group (-OO-), such as peracetic acid and perchromic acid.

[0189] Suitable percompounds containing at least one peroxide group include, but are not limited to, peracetic acid or its salts, percarbonates, and organic peroxides such as benzoyl peroxide, urea hydrogen peroxide, and / or di-tert-butyl peroxide.

[0190] Suitable percompounds containing at least one peroxide group include peroxides. As used herein, the term "peroxide" includes ROOR', wherein R and R' are each independently H, C 1 To C 6 Straight or branched chain alkyl, alkanol, carboxylic acid, ketone (for example) or amine, and each of the above may be independently substituted by one or more benzyl groups (for example benzoyl peroxide), which itself may be substituted by OH or C 1 -C 5 Alkyl substitution, and their salts and adducts. Thus, the term includes common examples such as hydrogen peroxide, peroxyformic acid, peroxyacetic acid, peroxypropionic acid, substituted or unsubstituted peroxybutyric acid, hydroperoxide-acetaldehyde, and the term also encompasses common peroxide complexes such as urea peroxide.

[0191] Suitable percompounds containing at least one peroxy group include persulfates. As used herein, the term "persulfate" includes monopersulfates, dipersulfates and acids and salts and adducts thereof. This includes, for example, peroxydisulfates, peroxymonosulfuric acid and / or peroxymonosulfate, peroxomonosulfate, peroxo acid, including, for example, salts such as potassium peroxymonosulfate, but preferably non-metallic salts such as ammonium peroxymonosulfate.

[0192] Suitable percompounds containing at least one peroxy group include perphosphates as defined above, and include peroxydiphosphates.

[0193] Additionally, ozone is a suitable oxidant, alone or in combination with one or more other suitable oxidants.

[0194] Suitable per-compounds that do not contain a peroxy group include, but are not limited to, periodic acid and / or any salt of periodic acid (hereinafter referred to as "periodates"), perchloric acid and / or any salt of perchloric acid (hereinafter referred to as "perchlorates"), perbromic acid and / or any salt of perbromic acid (hereinafter referred to as "perbromates"), and perboric acid and / or any salt of perboric acid (hereinafter referred to as "perborates").

[0195] Other oxidizing agents are also suitable components of the compositions of the present invention. Iodates are useful oxidizing agents.

[0196] Two or more oxidizing agents may be combined to obtain synergistic performance benefits.

[0197] In most embodiments of the present invention, the oxidant is selected from peroxy compounds selected from hydrogen peroxide, urea peroxide, peroxyformic acid, peroxyacetic acid, peroxypropionic acid, substituted or unsubstituted peroxybutyric acid, hydroperoxide-acetaldehyde, potassium periodate, ammonium peroxymonosulfate; and non-peroxy compounds selected from ferric nitrite, KClO 4 , KBrO 4 、KMnO 4 .

[0198] In some embodiments, the preferred oxidizing agent is hydrogen peroxide.

[0199] The oxidant concentration may range from about 0.01 wt % to 30 wt %, with a preferred concentration of the oxidant being about 0.1 wt % to 20 wt %, and a more preferred concentration of the oxidant being about 0.5 wt % to about 10 wt %. The weight percentages are relative to the composition.

[0200] Activator

[0201] An activator or catalyst is a material that interacts with the oxidant and promotes the formation of free radicals by at least one free radical generating compound present in the fluid.

[0202] The activator may be a metal-containing compound, in particular the metal is selected from metals known to activate the Fenton reaction process in the presence of an oxidizing agent such as hydrogen peroxide.

[0203] The activator may be a non-metal containing compound. Iodine may be used, for example, with hydrogen peroxide to form free radicals.

[0204] If the activator is a metal ion or metal-containing compound, it is a thin layer associated with the solid surface in contact with the fluid. If the activator is a non-metal-containing substance, it can be dissolved in the fluid. It is preferred that the activator is present in an amount sufficient to promote the desired reaction.

[0205] Activators include, but are not limited to (1) inorganic oxide particles coated with a transition metal on the surface thereof, wherein the transition metal is selected from iron, copper, manganese, cobalt, cerium and combinations thereof; (2) soluble catalysts include, but are not limited to iron (III) nitrate, iron (III) ammonium oxalate trihydrate, iron (III) citrate monohydrate, iron (III) acetylacetonate and ethylenediaminetetraacetic acid, iron (III) sodium salt hydrate, metal compounds with multiple oxidation states selected from Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V; and combinations thereof.

[0206] The amount of activator in the slurry is in the range of about 0.00001 wt % to 5 wt %, preferably about 0.0001 wt % to 2.0 wt %, more preferably about 0.0005 wt % to 1.0 wt %; and most preferably 0.001 wt % to 0.5 wt %.

[0207] water

[0208] The polishing composition is water-based and therefore contains water. In the composition, water functions in various ways, such as, for example, dissolving one or more solid components of the composition, acting as a carrier for the components, as an aid in removing polishing residues, and as a diluent. Preferably, the water used in the cleaning composition is deionized (DI) water.

[0209] It is believed that for most applications, water comprises, for example, about 10 to about 90 weight % or 90 weight % water. Other preferred embodiments may comprise about 30 to about 95 weight % water. Yet other preferred embodiments may comprise about 50 to about 90 weight % water. Yet other preferred embodiments may include an amount of water to achieve the desired weight percentages of the other ingredients.

[0210] Corrosion inhibitor (optional)

[0211] The corrosion inhibitors used in the CMP compositions disclosed herein include, but are not limited to, nitrogen-containing cyclic compounds such as 1,2,3-triazole, 1,2,4-triazole, 1,2,3-benzotriazole, 5-methylbenzotriazole, benzotriazole, 1-hydroxybenzotriazole, 4-hydroxybenzotriazole, 3-amino-1,2,4-triazole, 4-amino-4H-1,2,4-triazole, 5-aminotriazole, benzimidazole, benzothiazoles such as 2,1,3-benzothiadiazole, triazinethiol, triazinedithiol and triazinetrithiol, pyrazoles, imidazoles, isocyanurates such as 1,3,5-tris(2-hydroxyethyl)isocyanurate and combinations thereof. Preferred inhibitors are 1,2,4-triazole, 5-aminotriazole and 1,3,5-tris(2-hydroxyethyl)isocyanurate.

[0212] The amount of corrosion inhibitor in the slurry ranges from less than 1.0 wt%, preferably less than 0.5 wt% or more preferably less than 0.25 wt%.

[0213] Sag reducer (optional)

[0214] The CMP composition may further comprise a dishing reducing agent or dishing reducing agent selected from the group consisting of sarcosinates and related carboxylic acid compounds; hydrocarbon-substituted sarcosinates; amino acids; organic polymers and copolymers having molecules containing ethylene oxide repeating units, such as polyethylene oxide (PEO); ethoxylated surfactants; nitrogen-containing heterocycles without nitrogen-hydrogen bonds; sulfides; oxazolidines or mixtures of functional groups in one compound; nitrogen-containing compounds having three or more carbon atoms that form alkylammonium ions; aminoalkyl groups having three or more carbon atoms; polymer corrosion inhibitors containing at least one nitrogen-containing heterocycle or a repeating group of a tertiary or quaternary nitrogen atom; polycationic amine compounds; cyclodextrin compounds; polyethyleneimine compounds; glycolic acid; chitosan; sugar alcohols; polysaccharides; alginate compounds; sulfonic acid polymers. Glycine is a preferred dishing reducing agent.

[0215] When present, the dishing reducing agent is present in an amount ranging from about 0.001 wt % to 2.0 wt %, preferably 0.005 wt % to 1.5 wt %, more preferably 0.01 wt % to 1.5 wt %, based on the weight of the total CMP composition.

[0216] Stabilizer (optional)

[0217] The composition may also include one or more of various optional additives. Suitable optional additives include stabilizing agents. These optional additives are generally used to promote or enhance the stability of the composition for sedimentation, flocculation (including precipitation, aggregation or agglomeration of particles, etc.) and decomposition. Stabilizers can be used to extend the shelf life of oxidants (including compounds that generate free radicals) by isolating activator materials, by quenching free radicals, or by stabilizing compounds that form free radicals in addition.

[0218] Some materials can be used to stabilize hydrogen peroxide. An exception to metal contamination is the presence of selected stable metals, such as tin. In some embodiments of the present invention, a small amount of tin may be present, typically less than about 25ppm, for example, between about 3 to about 20ppm. Similarly, zinc is also commonly used as a stabilizer. In some embodiments of the present invention, zinc may be present in a small amount, typically less than about 20ppm, for example, between about 1 to about 20ppm. In another preferred embodiment, the fluid composition contacting the substrate has less than 500ppm, for example, less than 100ppm of dissolved metals with multiple oxidation states, except tin and zinc. In the most preferred commercial embodiment of the present invention, the fluid composition contacting the substrate has less than 9ppm of dissolved metals with multiple oxidation states, for example, less than 2ppm of dissolved metals with multiple oxidation states, except tin and zinc. In some preferred embodiments of the present invention, the fluid composition contacting the substrate has less than 50ppm, preferably less than 20ppm, more preferably less than 10ppm of dissolved total metals (except tin and zinc).

[0219] Because metals in solution are generally discouraged, preferred are those non-metal containing oxidants that are typically present in salt form (eg, persulfates), acid form, and / or ammonium salt form (eg, ammonium persulfate).

[0220] Other stabilizers include free radical quenchers. As discussed, these will weaken the effectiveness of the free radicals generated. Therefore, if present, it is preferred that they are present in small amounts. Most antioxidants, i.e., vitamin B, vitamin C, citric acid, etc., are free radical quenchers. Most organic acids are free radical quenchers, but three organic acids that are effective and have other beneficial stabilizing properties are phosphonic acid, the binder oxalic acid, and the non-radical scavenging chelator gallic acid.

[0221] In addition, it is believed that carbonates and phosphates bind to the activator and hinder fluid contact. Carbonates are particularly useful because they can be used to stabilize the slurry, but small amounts of acid can quickly remove the stabilizing ions. Stabilizers that can be used for adsorbed activators can be film formers that form a film on the silica particles.

[0222] Suitable stabilizers include organic acids such as adipic acid, phthalic acid, citric acid, malonic acid, phthalic acid; and phosphoric acid; substituted or unsubstituted phosphonic acids, i.e., phosphonic acid compounds; nitriles; and other ligands, such as those that bind to activator materials and thereby reduce reactions that degrade oxidants, and any combination of the foregoing agents. As used herein, an acid stabilizing agent refers to an acid stabilizer and its conjugate base. That is, various acid stabilizing agents may also be used in their conjugated form. For example, here, for the above-mentioned acid stabilizing agents, adipic acid stabilizing agents include adipic acid and / or its conjugate base, and carboxylic acid stabilizing agents include carboxylic acids and / or its conjugate base, carboxylates, and the like. Suitable stabilizers used alone or in combination with one or more other stabilizers reduce the rate at which oxidants such as hydrogen peroxide decompose when mixed into the CMP slurry.

[0223] On the other hand, the presence of stabilizers in the composition may impair the efficacy of the activator. Its amount should be adjusted to match the desired stability while having the lowest adverse effect on the effectiveness of the CMP system. Generally, any of these optional additives should be present in an amount sufficient to substantially stabilize the composition. The necessary amount varies depending on the specific additive selected and the specific composition of the CMP composition, such as the surface properties of the abrasive component. If too little additive is used, the additive has little or no effect on the stability of the composition. On the other hand, if too much additive is used, the additive may cause undesirable foam and / or flocculants to form in the composition.

[0224] Typically, suitable amounts of these stabilizers range from about 0.0001 to 5 weight percent, preferably about 0.00025 to 2 weight percent, more preferably about 0.0005 to about 1 weight percent relative to the composition. The stabilizer can be added directly to the composition or applied to the surface of the abrasive component of the composition.

[0225] pH adjuster (optional)

[0226] The compositions disclosed herein include a pH adjusting agent. A pH adjusting agent is generally used in the compositions disclosed herein to increase or decrease the pH of the polishing composition. The pH adjusting agent can be used to improve the stability of the polishing composition, adjust the ionic strength of the polishing composition, and improve the safety of operation and use as needed.

[0227] Suitable pH adjusters for lowering the pH of the polishing composition include, but are not limited to, nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids, and mixtures thereof. Suitable pH adjusters for raising the pH of the polishing composition include, but are not limited to, potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and mixtures thereof.

[0228] When used, the amount of pH adjuster is preferably in the range of about 0.01 wt. % to about 5.0 wt. % relative to the total weight of the polishing composition. A preferred range is about 0.01 wt. % to about 1 wt. % or about 0.05 wt. % to about 0.15 wt. %.

[0229] The pH of the slurry is between 1 and 14, preferably between 1 and 7, more preferably between 1 and 6, most preferably between 1.5 and 4.

[0230] Surfactant (optional)

[0231] The compositions disclosed herein optionally include surfactants, which in part help protect the wafer surface during and after polishing to reduce defects in the wafer surface. Surfactants can also be used to control the removal rate of some films (such as low-K dielectrics) used in polishing. Suitable surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof.

[0232] The nonionic surfactant can be selected from a range of chemical types including, but not limited to, long chain alcohols, ethoxylated alcohols, ethoxylated acetylenic glycol surfactants, polyethylene glycol alkyl ethers, propylene glycol alkyl ethers, glucoside alkyl ethers, polyethylene glycol octylphenyl ethers, polyethylene glycol alkylphenyl ethers, glycerol alkyl esters, polyoxyethylene glycol sorbitan alkyl esters, sorbitan alkyl esters, cocamide monoethanolamine, cocamide diethanolamine dodecyldimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amines, and fluorinated surfactants.

[0233] The molecular weight of surfactants can range from a few hundred to over a million. The viscosities of these materials also have a very wide distribution.

[0234] Anionic surfactants include, but are not limited to, salts with suitable hydrophobic tails, such as alkyl carboxylates, alkyl polyacrylates, alkyl sulfates, alkyl phosphates, alkyl dicarboxylates, alkyl hydrogen sulfates, alkyl hydrogen phosphates, such as alkoxy carboxylates, alkoxy sulfates, alkoxy phosphates, alkoxy dicarboxylates, alkoxy hydrogen sulfates, alkoxy hydrogen phosphates, such as substituted aryl carboxylates, substituted aryl sulfates, substituted aryl phosphates, substituted aryl dicarboxylates, substituted aryl hydrogen sulfates and substituted aryl hydrogen phosphates, etc. The counter ions of this type of surfactant include, but are not limited to potassium, ammonium and other positive ions. The molecular weight of these anionic surface wetting agents ranges from hundreds to hundreds of thousands.

[0235] Cationic surfactants carry a positive charge over the major part of the molecular framework. Cationic surfactants are usually halides of molecules containing a hydrophobic chain and a cationic charge center such as amines, quaternary ammonium, benzyalkonium and alkylpyridinium ions.

[0236] On the other hand, the surfactant can be an amphoteric surfactant, which has positive (cationic) and negative (anionic) charges on the main molecular chain, and carries their relative counterions. The cationic part is based on primary, secondary or tertiary amines or quaternary ammonium cations. The anionic part can be more variable and includes sulfonates, such as in sulfobetaine CHAPS (3-[(3-cholamidopropyl) dimethylammonium]-1-propanesulfonate) and cocamidopropyl hydroxysulfobetaine. Betaines such as cocamidopropyl betaine have carboxylic acid and ammonium. Some amphoteric surfactants can have phosphate anions and amines or ammonium, such as the phospholipids phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine and sphingomyelin.

[0237] Examples of surfactants also include, but are not limited to, sodium lauryl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, secondary alkyl sulfonates, alcohol ethoxylates, acetylenic surfactants, and any combination thereof. Examples of suitable commercially available surfactants include TRITON manufactured by Dow Chemicals. TM , Tergitol TM 、DOWFAX TM Surfactant family and SURFYNOL manufactured by Air Products and Chemicals TM 、DYNOL TM , Zetasperse TM 、Nonidet TM and Tomadol TM Various surfactants in the surfactant family. Suitable surfactants among surfactants may also include polymers containing ethylene oxide (EO) and propylene oxide (PO) groups. Examples of EO-PO polymers are Tetronic from BASF Chemicals. TM 90R4.

[0238] When used, the amount of surfactant is generally in the range of 0.0001 wt % to about 1.0 wt % relative to the total weight of the barrier CMP composition. When used, the preferred range is from about 0.010 wt % to about 0.1 wt %.

[0239] Chelating agent (optional)

[0240] Chelating agents may be optionally used in the compositions disclosed herein to enhance the affinity of the chelating ligand for the metal cation. Chelating agents may also be used to prevent the accumulation of metal ions on the polishing pad (which can lead to polishing pad contamination and instability in the removal rate). Suitable chelating agents include, but are not limited to, for example, amine compounds such as ethylenediamine, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA); aromatic acids such as benzenesulfonic acid, 4-toluenesulfonic acid, 2,4-diamino-benzenesulfonic acid, etc.; non-aromatic organic acids such as itaconic acid, malic acid, malonic acid, tartaric acid, citric acid, oxalic acid, gluconic acid, lactic acid, mandelic acid or their salts; various amino acids and their derivatives, such as glycine, serine, proline, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan, valine, arginine, aspartic acid, threonine, tryptophan, valine, arginine, threon ... Asparagine, aspartic acid, cysteine, glutamic acid, glutamine, ornithine, selenocysteine, tyrosine, sarcosine, N-bicine, N-tricine, acetylglutamine, N-acetylaspartic acid, acetylcarnitine, acetylcysteine, N-acetylglutamic acid, acetylleucine, acivicin, S-adenosyl-L-homocysteine, agaricin, alanosine, aminohippuric acid, L-arginine ethyl ester, aspartame, aspartylglucosamine, benzylmercaptouric acid, ε-N-biotinyl-L-lysine, briannib alanine ester, carboxymethylcysteine, N (6)-Carboxymethyl lysine, cargotyrosine, cilastatin, citivotone, coprine, dibromotyrosine, dihydroxyphenylglycine, eflornithine, phenclonin, 4-fluoro-L-threonine, N-formylmethionine, γ-L-glutamyl-L-cysteine, 4-(γ-glutamylamino)butyric acid, glutaurine, guanidinoacetic acid, hadacidin, hepapressin, lisinopril, lysine, N-methyl-D-aspartic acid, N-methyl-L-glutamyl Amine, Milacetamide, Nitrosoproline, Nocardin A, Nopaline, Octopine, Ombrabulin, Openic Acid, Anthranilic Acid, Oxacerol, Polylysine, Remacemide, Salicylic Acid, Serine, Stampidine, Pseudomonas toxin, Tetrazolylglycine, Thiophane, Thymectacin, Tiopronin, Tryptophan Tryptophan Quinone, Valacyclovir, Valganciclovir and phosphonic acid, and derivatives thereof, such as, for example, octylphosphonic acid, aminobenzylphosphonic acid, and combinations and salts thereof.

[0241] Where chemical bonding is desired, for example, copper and tantalum cations, chelating agents may be used to accelerate the dissolution of copper and tantalum oxides to produce the desired removal rates of copper lines, vias or trenches and barrier layers or films.

[0242] When used, the amount of chelating agent preferably ranges from about 0.01 wt % to about 3.0 wt %, more preferably from about 0.4 wt % to about 1.5 wt %, relative to the total weight of the composition.

[0243] Biocide (optional)

[0244] The CMP formulations disclosed herein may also contain additives to control biological growth, such as biocides. Some additives to control biological growth are disclosed in U.S. Patent No. 5,230,833 and U.S. Patent Application Publication No. 2002 / 0025762, which are incorporated herein by reference. Biological growth inhibitors include, but are not limited to, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, alkylbenzyldimethylammonium chloride and alkylbenzyldimethylammonium hydroxide, wherein the alkyl chain ranges from 1 to about 20 carbon atoms, sodium chlorite, sodium hypochlorite, isothiazolinone compounds such as methylisothiazolinone, methylchloroisothiazolinone and benzisothiazolinone. Some commercially available preservatives include KATHON from Dow Chemicals TM and NEOLENE TM Product family and Preventol from Lanxess TM family.

[0245] Preferred biocides are isothiazolinone compounds such as methylisothiazolinone, methylchloroisothiazolinone and benzisothiazolinone.

[0246] The CMP polishing composition optionally comprises a biocide in a range of 0.0001 wt. % to 0.10 wt. %, preferably 0.0001 wt. % to 0.005 wt. %, more preferably 0.0002 wt. % to 0.0025 wt. % to prevent bacterial and fungal growth during storage.

[0247] The compositions disclosed herein can be manufactured in concentrated form and subsequently diluted with deionized water when used. Other components, such as, for example, oxidants, can be retained in the form of concentrates and added when used to minimize incompatibilities between components in the concentrate form. The compositions disclosed herein can be manufactured in two or more components, which can be mixed before use.

[0248] Working Example

[0249] General experimental process

[0250] Unless otherwise indicated, all percentages are by weight.

[0251] Part I. Synthesis of polycationic polymers or copolymers

[0252] The present invention includes several controlled radical polymerization techniques such as reversible addition-fragmentation chain transfer polymerization (RAFT). By using this controlled process, specific design of materials with optimized molecular weight and polydispersity is possible, which is a distinct distinguishing feature from other described polymers in CMP applications.

[0253] Unless otherwise stated, all reagents and solvents were purchased from Sigma-Aldrich (Merck) of the highest commercial grade and used as received.

[0254] Characterization methods

[0255] NMR spectra were recorded on a 500 MHz Bruker Avance II+ spectrometer using deuterated solvents from Sigma-Aldrich (Merck). Chemical shifts are reported as d values ​​(ppm) and are relative to the internal standard Si(OMe) 4 (0.00ppm) calibration.

[0256] The samples were cultured at 40 °C in HO containing 10 mM sodium acetate. 2 The polycationic polymers were analyzed by size exclusion chromatography (SEC) (flow rate: 0.5 mL / min) run in 0.5% HCl / MeOH / EtOAc (54 / 23 / 23, v / v / v). The measurements were performed on an Agilent 1260 HPLC equipped with a column set consisting of a PSS Novema precolumn and a PSS Novema MAX ultra-high column. The samples were dissolved in an eluent containing 0.1% ethylene glycol as an internal standard at 50°C. The average molar mass of the polymer was derived from the refractive index signal based on a poly(2-vinylpyridine) calibration curve.

[0257] Example 1: Poly(vinyl-3-ethyl-1H-imidazol-3-ium-co-tributyl-(4-vinylbenzyl)-phosphonium) bromide chloride

[0258]

[0259] Monomer Synthesis A:

[0260]

[0261] Ethyl bromide (45.8 g, 420.8 mmol) was dissolved in acetonitrile (100 mL). 1-vinyl imidazole (20 g, 210 mmol) was added dropwise at room temperature. The reaction mixture was then stirred at 60 ° C for 12 h, cooled to room temperature and added to ethyl acetate (1.2 L), whereby a white solid was precipitated. The solid was washed 3 times with ethyl acetate and dried in vacuo (38 g, 89% yield).

[0262] 1H NMR (500 MHz, DMSO-d 6 )δ:9.60(t,J=1.6Hz,1H),8.23(t,J=1.9Hz,1H),7.98(t,J=1.8Hz,1H),7.32(dd,J=15.7,8.7Hz,1H),5. 99(dd,J=15.7,2.4Hz,1H), 5.43(dd,J=8.7,2.3Hz,1H), 4.25(q,J=7.3Hz,2H), 1.46(t,J=7.3Hz,3H)ppm.

[0263] Monomer synthesis B:

[0264]

[0265] 4-vinylbenzyl chloride (CAS:1592-20-7, 10g, 123mmol) is dissolved in 233mL anhydrous acetone. Tributylphosphane (CAS:998-40-3, 25g, 123mmol) is added and the reaction mixture is stirred for 18h under reflux. The product is precipitated by adding methyl tert-butyl ether (MTBE, 1.2L) in the cooling solution. The solid is filtered, washed twice with 100mL MTBE and vacuum dried to obtain a white solid (35g, 80% yield).

[0266] 1 H NMR (500MHz, D 2 O): δ=7.55(d,J=8.0Hz,2H),7.31(dd,J=8.3,2.5Hz,2H),6.81(dd,J=17.7,11.0Hz,1H),5.89(dd,J=17.8,1.0Hz,1H),5.40-5.34(m ,2H),3.67(d,J=14.6Hz,2H),2.18-2.08(m,6H),1.54(dq,J=10.1,7.3Hz,6H),1.45(hept,J=7.1Hz,6H),0.92(t,J=7.3Hz,9H)ppm.

[0267] polymerization:

[0268]

[0269] Monomer A (2.5 g, 12.3 mmol), monomer B (4.4 g, 12.3 mmol), AIBN (CAS: 78-67-1, 3.8 mg, 0.023 mmol) and 2-(dodecylthiocarbonylsulfonylthio)-2-methylpropionic acid (DDMAT, CAS: 461642-78-4, 25 mg, 0.07 mmol) were loaded into a Schlenk flask. The mixture was dissolved in acetonitrile / water (50 mL, 1: 1 v / v), purged with Ar for 30 min, and then heated at 65 ° C for 18 h. The solution was cooled to room temperature, acetonitrile was removed, and the residue was dissolved in 10 mL of dichloromethane. Finally, the polymer was precipitated by adding 100 mL of THF, washed twice with THF and dried in vacuo to obtain 5.0 g of a yellow solid (72% yield).

[0270] 1 H NMR (500 MHz, DMSO-d 6 )δ:9.81(width s),7.31(width s),6.41(width s),4.20(width s),2.30(width s),1.33(width s),0.85(width s)ppm.

[0271] SEC: Mn: 16.2kDa; Mw: 40.9kDa; PDI: 2.5

[0272] Some IICMP experiments

[0273] Use the phosphonium-based polymer synthesized in Part I

[0274] The polishing compositions and related methods described herein are effectively used for CMP of a wide variety of substrates, including most substrates, and are particularly useful for polishing tungsten substrates.

[0275] In the examples given below, CMP experiments were carried out using the procedures and experimental conditions given below.

[0276] parameter:

[0277] Angstrom - unit of length

[0278] BP: back pressure, in psi

[0279] CMP: Chemical Mechanical Planarization = Chemical Mechanical Polishing

[0280] CS: Carrier speed

[0281] DF: Downforce: The pressure applied during CMP, in psi

[0282] min: minutes

[0283] ml: milliliters

[0284] mV: millivolt

[0285] psi: pounds per square inch

[0286] PS: The platen speed of the polishing equipment, in rpm (revolutions per minute)

[0287] SF: polishing composition flow rate, ml / min

[0288] TEOS: Silicon oxide film deposited by chemical vapor deposition (CVD) using tetraethyl orthosilicate as a precursor

[0289] Weight %: weight percentage (of the listed components)

[0290] Removal rate (RR) = (film thickness before polishing - film thickness after polishing) / polishing time.

[0291] Removal rate and selectivity

[0292] Tungsten removal rate: Tungsten removal rate measured at 2.5 psi down pressure of the CMP equipment.

[0293] TEOS removal rate: TEOS removal rate measured at a given down pressure. The down pressure of the CMP tool was 2.5 psi.

[0294] SiN removal rate: SiN removal rate measured at a given down pressure. The down pressure of the CMP equipment was 2.5 psi.

[0295] The CMP equipment used in the examples is AMAT 200mm It is manufactured by Applied Materials, Inc. 3050 Bowers Avenue, Santa Clara, California, 95054. An IC1010 polishing pad supplied by Dow Chemicals was used on the platen for the polishing studies.

[0296] 200 mm diameter silicon wafers coated with tungsten film, TEOS film, SiN film or SKW patterned structure containing tungsten were obtained from SKW Associate, Inc. 2920 Scott Blvd, Santa Clara, CA 95054. The polishing time for blanket film was one minute. The tungsten removal rate was measured using a sheet resistance measurement technique. The removal of TEOS was measured using an optical technique. The patterned wafers were polished on an Ebara polisher for a period of time based on eddy current technology. The polishing time of the patterned wafer exceeded the endpoint determined by the eddy current endpoint technique by 15 seconds. The patterned wafers were analyzed using a KLA Tencor P15 profiler (large feature size) or an AFM tool (small feature size).

[0297] Polishing was performed using a platen speed of 111 RPM, a carrier speed of 113 RPM, a slurry flow rate of 200 ml / min, and a down force of 2.5 psi.

[0298] During the polishing process, a substrate (e.g., blanket W or patterned W wafer) is placed face down on a polishing pad that is fixedly attached to a rotatable platen of a CMP polisher. In this way, the substrate to be polished and planarized is in direct contact with the polishing pad. A wafer carrier system or polishing head is used to hold the substrate in place and to apply downward pressure to the back of the substrate as the platen and substrate rotate during the CMP process. During the CMP process, a polishing composition (slurry) is applied (usually continuously) to the polishing pad to effectively remove material and planarize the substrate.

[0299] In the following working examples, a reference CMP (without polycationic polymer) slurry was prepared with 0.01 wt % ferric nitrate (iron (III) nitrate), 0.08 wt % malonic acid (stabilizer), 2.0 wt % hydrogen peroxide, 0.1 wt % glycine, and 0.25 wt % Fuso PL-2C silica particles in water and the pH was adjusted to 2.3 with nitric acid.

[0300] Working CMP slurries were prepared by adding 10 ppm and 20 ppm of poly(vinyl-3-ethyl-1H-imidazol-3-ium-co-tributyl-(4-vinylbenzyl)-phosphonium) bromide chloride prepared in Example 1 to the reference CMP slurry, respectively.

[0301] The effects of polycationic polymers on removal rate, selectivity, erosion, and dishing of tungsten, TEOS, and SiN were tested.

[0302] The removal rates and selectivities of W:TEOS and W:SiN are shown in Table 1.

[0303] Table 1. Membrane removal rate and membrane selectivity

[0304]

[0305] As shown in Table 1, the working CMP slurry with a small amount of polycationic polymer suppresses the removal rates of TEOS and SiN while maintaining the removal rate of W, thus improving the selectivity.

[0306] Table 2. Comparison of W recess (50x50μm) and erosion (7x3μm)

[0307]

[0308] The dishing and erosion data were determined for different patterned structures with different line features at 20% overpolish using Example 1 (dishout: 50 / 50 μm; erosion: 7 / 3 μm). The values ​​for high density features are summarized in Table 2.

[0309] As shown in Table 2, the working CMP slurry with a small amount of polycationic polymer inhibited dishing and erosion of the patterned structures tested.

[0310] Although the principles of the present invention have been described above in conjunction with preferred embodiments, it should be clearly understood that such description is merely exemplary and not intended to limit the scope of the present invention. On the contrary, the subsequent detailed description of the preferred exemplary embodiments will provide a description of the preferred exemplary embodiments of the present invention for those skilled in the art. Various changes may be made to the functions and arrangements of the elements without departing from the spirit and scope of the present invention as set forth in the appended claims.

Claims

1. A polycationic polymer or copolymer formed from at least one first cationic monomer and at least one second cationic monomer; in The at least one first cationic monomer comprises the structure of (I): in: P1 represents a polymerizable group; Sp1 represents a spacer group or a single bond; R1, R2, R3 are each independently H; or a substituted or unsubstituted aliphatic, aromatic, heteroaromatic or siloxane moiety, wherein CH2 not in an aromatic or heteroaromatic ring may be replaced by O, S or N in a manner that there are no heteroatoms attached to each other; and wherein hydrogen may be replaced by F, Cl or CN; R4 is a substituted or unsubstituted straight chain, cyclic or branched aliphatic group; X - represents anionic counterions; as well as The at least one second cationic monomer comprises the structure of (II): in: P2 represents a polymerizable group; Sp2 represents a spacer group or a single bond and can be selected from linear, branched and cyclic alkyl groups; wherein CH2 not in an aromatic or heteroaromatic ring can be replaced by O, S or N in a manner without heteroatoms being connected to each other, and hydrogen can be replaced by F, Cl or CN; R1, R2, R3 are each independently substituted or unsubstituted aliphatic, cycloaliphatic or branched aliphatic, aromatic or heteroaromatic, wherein CH2 not in an aromatic or heteroaromatic ring may be replaced by O, S or N in a manner without heteroatoms attached to each other; and wherein hydrogen may be replaced by F, Cl or CN; and X - represents anionic counter ions.

2. The polycationic polymer or copolymer according to claim 1, wherein at least one of the polymerizable groups P1 and P2 is selected from groups containing a C=C double bond.

3. A polycationic polymer or copolymer according to any one of claims 1 to 2, wherein the anionic counterions in (I) and (II) may be the same or different and are each selected from F-, Cl-, Br-, I-, BF4-, PF6-, carboxylate, malonate, citrate, carbonate, fumarate, MeOSO3-, MeSO3-, CF3COO-, CF3SO3-, nitrate and sulfate.

4. The polycationic polymer or copolymer according to any one of claims 1 to 3, wherein the at least one first cationic monomer comprises a crosslinkable structure comprising R5, wherein R5 is selected from formula (a): -Sp3-P3 (a) in: Sp3 represents a spacer group or a single bond at each occurrence and may be selected from linear, branched and cyclic alkyl groups; wherein CH2 may be replaced by O, S or N in a manner that no heteroatoms are attached to each other, and hydrogen may be replaced by F, Cl or CN; and P3 is a polymerizable group which may be the same as or different from P1.

5. The polycationic polymer or copolymer according to any one of claims 1 to 4, wherein the polycationic polymer or copolymer is formed by a polymerization process selected from the group consisting of free radical polymerization, reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP), atom transfer reaction polymerization (ATRP), ring-opening polymerization (ROMP) and polycondensation.

6. The polycationic polymer or copolymer according to any one of claims 1 to 5, wherein the polycationic polymer or copolymer is poly(vinyl-3-ethyl-1H-imidazol-3-ium-co-tributyl-(4-vinylbenzyl)-phosphonium) bromide chloride 7. A polycationic polymer or copolymer having at least one repeating unit of (A) and at least one repeating unit of (B): in: L represents a spacer group or a single bond at each occurrence; R1, R2 and R3 are each independently H or a substituted or unsubstituted aliphatic, aromatic, heteroaromatic or siloxane moiety; n is an integer from 1 to 500; and X - represents anionic counterions; in L represents a spacer group or a single bond at each occurrence; R1 and R2 are each a substituted or unsubstituted aliphatic, aromatic, or heteroaromatic moiety; m is an integer from 1 to 500; and X - represents anionic counter ions.

8. A polycationic polymer or copolymer according to claim 7, wherein the spacer group L is selected from substituted or unsubstituted straight chain, cyclic or branched aliphatic groups; wherein CH2 can be replaced by O, S or N in a manner without heteroatoms attached to each other, and wherein hydrogen can be replaced by F, Cl or CN.

9. A polycationic polymer or copolymer according to any one of claims 7-8, wherein the polycationic polymer or copolymer is formed by a polymerization process selected from the group consisting of free radical polymerization, reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP), atom transfer reaction polymerization (ATRP), ring-opening polymerization (ROMP) and polycondensation.

10. A chemical mechanical planarization composition comprising the polycationic polymer or copolymer according to any one of claims 1 to 9.

11. A chemical mechanical planarization composition comprising: an abrasive selected from the group consisting of inorganic oxide particles, inorganic oxide particles coated with metal oxides, organic polymer particles, organic polymer particles coated with metal oxides, and combinations thereof; Activator; Oxidants; An additive comprising a polycationic polymer or copolymer according to any one of claims 1 to 9; water; and optionally Corrosion inhibitors; Sag reducers; Stabilizers; pH adjuster.

12. The chemical mechanical planarization composition of claim 11, wherein the abrasive is in the range of 0.01 wt%-30 wt%, 0.05 wt%-20 wt%, 0.01 wt%-10 wt% or 0.1 wt%-2 wt%.

13. The chemical mechanical planarization composition of claim 11, wherein the additive comprising a polycationic polymer or copolymer ranges from 0.00001 wt% to 1.0 wt%, 0.0001 wt% to 0.5 wt%, 0.00025 wt% to 0.1 wt% or 0.0005 wt% to 0.05 wt%.

14. The chemical mechanical planarization composition of claim 11, wherein the abrasive is silica particles.

15. The chemical mechanical planarization composition of claim 11, wherein the oxidizing agent is selected from peroxy compounds selected from hydrogen peroxide, urea peroxide, peroxyformic acid, peroxyacetic acid, peroxypropionic acid, substituted or unsubstituted peroxybutyric acid, hydroperoxide-acetaldehyde, potassium periodate and ammonium peroxymonosulfate; and non-peroxy compounds selected from ferric nitrite, KClO4, KBrO4, KMnO4; and combinations thereof; and the range of the oxidizing agent is 0.01 wt%-30 wt%, 0.1 wt%-20 wt% or 0.5 wt%-10 wt%.

16. The chemical mechanical planarization composition of claim 11, wherein the activator is selected from (1) inorganic oxide particles having a transition metal coated on their surface; and the transition metal is selected from Fe, Cu, Mn, Co, Ce and combinations thereof; (2) a soluble catalyst selected from iron (III) nitrate, iron (III) ammonium oxalate trihydrate, iron (III) citrate monohydrate, iron (III) acetylacetonate and ethylenediaminetetraacetic acid, and iron (III) sodium salt hydrate; (3) a metal compound having multiple oxidation states selected from Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V; and combinations thereof; and the range of the activator is 0.00001 wt%-5.0 wt%, 0.0001 wt%-2.0 wt%, 0.0005 wt%-1.0 wt% or 0.001 wt%-0.5 wt%.

17. The chemical mechanical planarization composition of claim 11, wherein the corrosion inhibitor is selected from 1,2,3-triazole, 1,2,4-triazole, 1,2,3-benzotriazole, 5-methylbenzotriazole, benzotriazole, 1-hydroxybenzotriazole, 4-hydroxybenzotriazole, 3-amino-1,2,4-triazole, 4-amino-4H-1,2,4-triazole, 5-aminotriazole, benzimidazole, 2,1,3-benzothiadiazole, triazinethiol, triazinedithiol and triazinetrithiol, pyrazoles, imidazoles, isocyanurates such as 1,3,5-tris(2-hydroxyethyl) ester, and combinations thereof; and the corrosion inhibitor is in a range of less than 1.0 wt%, less than 0.5 wt%, or less than 0.25 wt%.

18. The chemical mechanical planarization composition of claim 11, wherein the pH adjuster is selected from (a) nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids and mixtures thereof to lower the pH; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine and mixtures thereof to increase the pH.

19. The chemical mechanical planarization composition of claim 11, wherein the pH of the composition is 1-14, 1-7, 1-6, or 1.5-4.

20. The chemical mechanical planarization composition of claim 11, wherein the dishing reducer is selected from the group consisting of sarcosinates and related carboxylic acid compounds; hydrocarbon-substituted sarcosinates; amino acids; organic polymers and copolymers having molecules containing ethylene oxide repeating units, such as polyethylene oxide (PEO); ethoxylated surfactants; nitrogen-containing heterocycles without nitrogen-hydrogen bonds; sulfides; oxazolidines or mixtures of functional groups in one compound; nitrogen-containing compounds having three or more carbon atoms that form alkylammonium ions; aminoalkyl groups having three or more carbon atoms; polymer corrosion inhibitors containing at least one nitrogen-containing heterocycle or a repeating group of a tertiary nitrogen or quaternary nitrogen atom; polycationic amine compounds; cyclodextrin compounds; polyethyleneimine compounds; glycolic acid; chitosan; sugar alcohols; polysaccharides; alginate compounds; and sulfonic acid polymers; and combinations thereof; and the dishing reducer ranges from 0.001 wt% to 2.0 wt%, 0.005 wt% to 1.5 wt% or 0.01 wt% to 1.0 wt%.

21. The chemical mechanical planarization composition of claim 11, wherein the stabilizer is selected from adipic acid, phthalic acid, citric acid, malonic acid, phthalic acid; phosphoric acid; substituted or unsubstituted phosphonic acid; nitriles; and combinations thereof; and the range of the stabilizer is 0.0001-5 wt%, 0.00025-2 wt% or 0.0005-1 wt%.

22. The chemical mechanical planarization composition of claim 11, wherein the chemical mechanical planarization composition comprises silica particles; poly(vinyl-3-ethyl-1H-imidazol-3-ium-co-tributyl-(4-vinylbenzyl)-phosphonium) bromide chloride, iron (III) nitrate, malonic acid, hydrogen peroxide and water; and the pH of the composition is 1.5-4.

23. A polishing method for chemical mechanical planarization of a semiconductor substrate comprising at least one tungsten-containing surface, comprising the steps of: a) providing a polishing pad; b) providing a chemical mechanical planarization composition comprising: an abrasive selected from the group consisting of inorganic oxide particles, inorganic oxide particles coated with metal oxides, organic polymer particles, organic polymer particles coated with metal oxides, and combinations thereof; Activator; Oxidants; An additive comprising a polycationic polymer or copolymer according to any one of claims 1 to 9; water; and optionally Corrosion inhibitors; Sag reducers; Stabilizers; pH adjusters; and c) polishing the at least one tungsten-containing surface with the chemical mechanical planarization composition.

24. The polishing method according to claim 23, wherein the chemical mechanical planarization composition has the abrasive in a range of 0.01 wt%-30 wt%, 0.05 wt%-20 wt%, 0.01 wt%-10 wt%, or 0.1 wt%-2 wt%.

25. The polishing method of claim 23, wherein the additive comprising a polycationic polymer or copolymer is in a range of 0.00001 wt% to 1.0 wt%, 0.0001 wt% to 0.5 wt%, 0.00025 wt% to 0.1 wt%, or 0.0005 wt% to 0.05 wt%.

26. The polishing method according to claim 23, wherein the abrasive is silica particles.

27. The polishing method according to claim 23, wherein the oxidizing agent is selected from peroxy compounds selected from hydrogen peroxide, urea peroxide, peroxyformic acid, peroxyacetic acid, peroxypropionic acid, substituted or unsubstituted peroxybutyric acid, hydroperoxide-acetaldehyde, potassium periodate and ammonium peroxymonosulfate; and non-peroxy compounds selected from ferric nitrite, KClO4, KBrO4, KMnO4; and combinations thereof; and the range of the oxidizing agent is 0.01 wt%-30 wt%, 0.1 wt%-20 wt% or 0.5 wt%-10 wt%.

28. The polishing method according to claim 23, wherein the activator is selected from (1) inorganic oxide particles having a transition metal coated on the surface thereof; and the transition metal is selected from Fe, Cu, Mn, Co, Ce and combinations thereof; (2) a soluble catalyst selected from iron (III) nitrate, iron (III) ammonium oxalate trihydrate, iron (III) citrate monohydrate, iron (III) acetylacetonate and ethylenediaminetetraacetic acid, and iron (III) sodium salt hydrate; (3) a metal compound having multiple oxidation states selected from Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V; and combinations thereof; and the range of the activator is 0.00001 wt%-5.0 wt%, 0.0001 wt%-2.0 wt%, 0.0005 wt%-1.0 wt% or 0.001 wt%-0.5 wt%.

29. The polishing method according to claim 23, wherein the corrosion inhibitor is selected from 1,2,3-triazole, 1,2,4-triazole, 1,2,3-benzotriazole, 5-methylbenzotriazole, benzotriazole, 1-hydroxybenzotriazole, 4-hydroxybenzotriazole, 3-amino-1,2,4-triazole, 4-amino-4H-1,2,4-triazole, 5-aminotriazole, benzimidazole, 2,1,3-benzothiadiazole, triazinethiol, triazinedithiol and triazinetrithiol, pyrazoles, imidazoles, isocyanurates such as 1,3,5-tris(2-hydroxyethyl) ester and combinations thereof; and the range of the corrosion inhibitor is less than 1.0 wt%, less than 0.5 wt% or less than 0.25 wt%.

30. The polishing method according to claim 23, wherein the pH adjuster is selected from (a) nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids and mixtures thereof to lower the pH; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine and mixtures thereof to increase the pH.

31. The polishing method according to claim 23, wherein the pH of the composition is 1-14, 1-7, 1-6, or 1.5-4.

32. The polishing method of claim 23, wherein the dishing reducing agent is selected from the group consisting of sarcosinates and related carboxylic acid compounds; hydrocarbon-substituted sarcosinates; amino acids; organic polymers and copolymers having molecules containing ethylene oxide repeating units, such as polyethylene oxide (PEO); ethoxylated surfactants; nitrogen-containing heterocycles without nitrogen-hydrogen bonds; sulfides; oxazolidines or mixtures of functional groups in one compound; nitrogen-containing compounds having three or more carbon atoms that form alkylammonium ions; aminoalkyl groups having three or more carbon atoms; polymer corrosion inhibitors containing at least one nitrogen-containing heterocycle or a repeating group of a tertiary or quaternary nitrogen atom; polycationic amine compounds; cyclodextrin compounds; polyethyleneimine compounds; glycolic acid; chitosan; sugar alcohols; polysaccharides; alginate compounds; and sulfonic acid polymers; and combinations thereof; and the dishing reducing agent ranges from 0.001 wt% to 2.0 wt%, 0.005 wt% to 1.5 wt% or 0.01 wt% to 1.0 wt%.

33. The polishing method according to claim 23, wherein the stabilizer is selected from adipic acid, phthalic acid, citric acid, malonic acid, phthalic acid; phosphoric acid; substituted or unsubstituted phosphonic acid; nitriles; and combinations thereof; and the range of the stabilizer is 0.0001-5 wt%, 0.00025-2 wt% or 0.0005-1 wt%.

34. The polishing method of claim 23, wherein the chemical mechanical planarization composition comprises silicon dioxide particles; iron (III) nitrate; malonic acid; hydrogen peroxide; poly (vinyl-3-ethyl-1H-imidazol-3-ium-co-tributyl-(4-vinylbenzyl)-phosphonium) bromide chloride, and water; and the pH of the composition is 1.5-4.

35. The polishing method of claim 23, wherein the at least one tungsten-containing surface comprises a recessed topography of less than 2000 angstroms or less than 1000 angstroms and an eroded topography of less than 2000 angstroms or less than 1000 angstroms.

36. A system for chemical mechanical planarization of a semiconductor substrate comprising at least one tungsten-containing surface, comprising: a) polishing pad; and b) a chemical mechanical planarization composition comprising: an abrasive selected from the group consisting of inorganic oxide particles, inorganic oxide particles coated with metal oxides, organic polymer particles, organic polymer particles coated with metal oxides, and combinations thereof; Activator; Oxidants; An additive comprising a cationic polymer or copolymer according to any one of claims 1 to 9; water; and optionally Corrosion inhibitors; Sag reducers; Stabilizers; pH adjuster; and The at least one tungsten-containing surface is contacted with the polishing pad and the chemical mechanical planarization composition, thereby polishing the at least one tungsten-containing surface with the chemical mechanical planarization composition.

37. The system of claim 36, wherein the chemical mechanical planarization composition has a range of 0.01 wt%-30 wt%, 0.05 wt%-20 wt%, 0.01 wt%-10 wt%, or 0.1 wt%-2 wt% of the abrasive.

38. The system of claim 36, wherein the additive comprising a polycationic polymer or copolymer ranges from 0.00001 wt% to 1.0 wt%, 0.0001 wt% to 0.5 wt%, 0.00025 wt% to 0.1 wt%, or 0.0005 wt% to 0.05 wt%.

39. The system of claim 36, wherein the abrasive is silica particles.

40. The system of claim 36, wherein the oxidant is selected from a peroxy compound selected from hydrogen peroxide, urea peroxide, performic acid, peracetic acid, perpropionic acid, substituted or unsubstituted perbutyric acid, hydroperoxide-acetaldehyde, potassium periodate, and ammonium permonosulfate; and a non-peroxy compound selected from ferric nitrite, KClO4, KBrO4, KMnO4; and combinations thereof; and the oxidant is in the range of 0.01 wt%-30 wt%, 0.1 wt%-20 wt%, or 0.5 wt%-10 wt%.

41. A system according to claim 36, wherein the activator is selected from (1) inorganic oxide particles having a transition metal coated on the surface thereof; and the transition metal is selected from Fe, Cu, Mn, Co, Ce and combinations thereof; (2) a soluble catalyst selected from iron (III) nitrate, iron (III) ammonium oxalate trihydrate, iron (III) citrate monohydrate, iron (III) acetylacetonate and ethylenediaminetetraacetic acid, and iron (III) sodium salt hydrate; (3) a metal compound having multiple oxidation states selected from Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V; and combinations thereof; and the range of the activator is 0.00001 wt%-5.0 wt%, 0.0001 wt%-2.0 wt%, 0.0005 wt%-1.0 wt% or 0.001 wt%-0.5 wt%.

42. The system of claim 36, wherein the corrosion inhibitor is selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, 1,2,3-benzotriazole, 5-methylbenzotriazole, benzotriazole, 1-hydroxybenzotriazole, 4-hydroxybenzotriazole, 3-amino-1,2,4-triazole, 4-amino-4H-1,2,4-triazole, 5-aminotriazole, benzimidazole, 2,1,3-benzothiadiazole, triazinethiol, triazinedithiol and triazinethiol, pyrazoles, imidazoles, isocyanurates such as 1,3,5-tris(2-hydroxyethyl) ester, and combinations thereof; and the corrosion inhibitor is in a range of less than 1.0 wt%, less than 0.5 wt%, or less than 0.25 wt%.

43. The system of claim 36, wherein the pH adjusting agent is selected from the group consisting of (a) nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids, and mixtures thereof, to lower the pH; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and mixtures thereof, to increase the pH.

44. The system of claim 36, wherein the pH of the composition is 1-14, 1-7, 1-6, or 1.5-4.

45. The system of claim 36, wherein the sag reducing agent is selected from the group consisting of sarcosinates and related carboxylic acid compounds; hydrocarbon-substituted sarcosinates; amino acids; organic polymers and copolymers having molecules containing ethylene oxide repeating units, such as polyethylene oxide (PEO); ethoxylated surfactants; nitrogen-containing heterocycles without nitrogen-hydrogen bonds; sulfides; oxazolidines or mixtures of functional groups in one compound; nitrogen-containing compounds having three or more carbon atoms that form alkylammonium ions; aminoalkyl groups having three or more carbon atoms; polymeric corrosion inhibitors containing at least one nitrogen-containing heterocycle or a repeating group of a tertiary or quaternary nitrogen atom; polycationic amine compounds; cyclodextrin compounds; polyethyleneimine compounds; glycolic acid; chitosan; sugar alcohols; polysaccharides; alginate compounds; and sulfonic acid polymers; and combinations thereof; and the sag reducing agent ranges from 0.001 wt% to 2.0 wt%, 0.005 wt% to 1.5 wt% or 0.01 wt% to 1.0 wt%.

46. ​​The system of claim 36, wherein the stabilizer is selected from adipic acid, phthalic acid, citric acid, malonic acid, phthalic acid; phosphoric acid; substituted or unsubstituted phosphonic acid; nitriles; and combinations thereof; and the range of the stabilizer is 0.0001-5 wt%, 0.00025-2 wt% or 0.0005-1 wt%.

47. The system of claim 36, wherein the chemical mechanical planarization composition comprises silicon dioxide particles; iron (III) nitrate; malonic acid; hydrogen peroxide; poly(vinyl-3-ethyl-1H-imidazol-3-ium-co-tributyl-(4-vinylbenzyl)-phosphonium) bromide chloride, and water; and the pH of the composition is 1.5-4.

Images