Guanidinium-based polyionic liquids and their use as additives for chemical mechanical planarization slurries

Abstract

The synthesis of a guanidinium-based polymer is disclosed. A chemical mechanical planarization (CMP) slurry contains an abrasive, an activator, an oxidizer, an additive containing a guanidinium-based polymer, and water. The use of the synthesized guanidinium-based polymer in the CMP slurry reduces dishing and erosion in highly selective tungsten slurries.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 377,626, filed September 29, 2022, the entire contents of which are incorporated herein by reference for all permissible purposes. [Background technology]

[0002] This disclosure relates to chemical mechanical planarization or polishing ("CMP") slurries (or compositions or formulations), polishing methods, and polishing systems for performing chemical mechanical planarization in the manufacture of semiconductor devices. In particular, this disclosure relates to polishing slurries suitable for use in polishing patterned semiconductor wafers that include tungsten-containing metallic materials.

[0003] Integrated circuits are interconnected using well-known multilayer interconnects. The interconnect structure typically includes a first layer of metallization, an interconnect layer, a second layer of metallization, and typically a third and subsequent layers of metallization. Interlayer dielectric materials, such as silicon dioxide, and sometimes low-k materials, are used to electrically isolate different layers of metallization within a silicon substrate or well. Electrical connections between different interconnect layers are made through the use of metallized vias, particularly tungsten vias. U.S. Pat. No. 4,789,648 describes a method for preparing multiple metallized layers and vias in an insulating film. Similarly, metal contacts are used to form electrical connections between interconnect layers and devices formed within the wells. Metal vias and contacts are typically filled with tungsten, and adhesion layers, such as titanium nitride (TiN) and / or titanium, are typically used to bond the metal layer, such as the tungsten metal layer, to the dielectric material.

[0004] In one semiconductor manufacturing process, metallized vias or contacts are formed by blanket tungsten deposition followed by a CMP step. In a typical process, a via hole is etched through an interlayer dielectric (ILD) to an interconnect line or semiconductor substrate. Next, a thin adhesion layer, such as titanium nitride and / or titanium, is typically formed on top of the ILD and directed into the etched via hole. A tungsten film is then blanket deposited on the adhesion layer and into the via. Deposition continues until the via hole is filled with tungsten. Finally, excess tungsten is removed by CMP to form the metal via.

[0005] In another semiconductor manufacturing process, tungsten is used as a gate electrode material for transistors because it has better electrical properties than polysilicon, which has traditionally been used as a gate electrode material, as taught by A. Yagishita et al., IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 47, NO. 5, MAY 2000.

[0006] Chemical mechanical polishing or planarization (CMP) has been used successfully in the manufacturing process of integrated circuits for decades. It is considered a key and enabling technology for the demands of miniaturization. While reducing defects during the CMP process has always been important, smaller feature sizes and devices at the 7 nm node and beyond impose even more stringent requirements on defect tolerance during polishing.

[0007] In a typical CMP process, the substrate is placed in direct contact with a rotating polishing pad. A carrier applies pressure against the backside of the substrate. During the polishing process, the pad and table are rotated while a downward force is maintained against the backside of the substrate. An abrasive, chemically reactive solution, commonly referred to as a polishing "slurry," "composition," or "formulation," is deposited on the pad during polishing, and the rotation and / or motion of the pad relative to the wafer transports 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. The polishing process is facilitated by the rotational motion of the pad relative to the substrate as the slurry is delivered to the wafer / pad interface. Polishing continues in this manner until the desired film on the insulator is removed. It is believed that tungsten removal in CMP is due to a synergistic effect of mechanical polishing and tungsten oxidation and subsequent dissolution.

[0008] Despite its relatively simple 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. For the most part, CMP technology is advancing faster than its underlying understanding, as described by Seo, J.A., review on chemical and mechanical phenomena at the wafer interface during chemical mechanical planarization. Journal of Materials Research 2021, 36(1), 235.

[0009] The importance of enabling technology for past and future demands for device scaling and new trends in the semiconductor industry is undeniable. Numerous interactions between the wafer, slurry, and pad, as well as overall process parameters, determine the outcome of CMP. Ultimately, material removal in CMP is the result of a complex interplay 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. Numerous materials are used in semiconductor device manufacturing, all of which require an optimized CMP process. Simultaneous polishing of completely different material combinations, such as dielectric materials, barrier layers, and metal layers, presents a real challenge for CMP.

[0010] Highly selective slurries have a large difference in metal removal rate versus dielectric removal rate and are of great interest for future industrial needs. However, there are imperfections associated with the use of these highly selective slurries. Metal layers can easily be over-polished, resulting in a "dishing" effect. Another unacceptable defect is called "erosion," which describes the difference in topography between areas with dielectric and dense arrays of metal vias or trenches.

[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.

[0012] Defect-reduced CMP process performance can be controlled through smart slurry design. Specially designed aqueous slurries are considered a major driver in 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. Generally, slurry compositions are complex combinations of abrasives and chemical components with different functions. Polymer additives play an important role in minimizing surface defects by interacting with certain materials. For example, positively charged polymers inhibit tungsten removal and can be used to reduce the dishing effect in tungsten CMP processes.

[0013] U.S. Pat. No. 5,876,490 describes the use of a polishing slurry containing abrasive particles, exhibiting a normal stress effect, and further containing a polyelectrolyte having ionic moieties of a different charge than those associated with the abrasive particles, the polyelectrolyte having a concentration of about 5 to about 50% by weight of the abrasive particles, and the polyelectrolyte having a molecular weight of about 500 to about 10,000.

[0014] U.S. Patent Application Publication No. 2010 / 0075501(A1) describes an aqueous chemical mechanical polishing dispersion used to polish a polishing target including a tungsten-containing interconnect layer. The aqueous chemical mechanical polishing dispersion includes (A) a cationic water-soluble polymer, (B) an iron(III) compound, and (C) colloidal silica particles. The content of the cationic water-soluble polymer (A) (M A ) (mass%) and the content of iron (III) compound (B) (M B ) (mass%) and "M A / M B =0.004 to 0.1”. The chemical mechanical polishing aqueous dispersion has a pH of 1 to 3.

[0015] U.S. Patent Application Publication No. 2010 / 0252774(A1) describes an aqueous dispersion for chemical mechanical polishing used to polish a polishing target including a wiring layer containing tungsten. The aqueous dispersion for chemical mechanical polishing contains (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 from the specific surface area by the BET method. The content (M) of the (A) cationic water-soluble polymer is 10 to 60 nm. A ) (mass%) and (C) the content of colloidal silica (M C ) (mass%) and "M A / M C =0.0001~0.003".

[0016] U.S. Patent Application Publication No. 2009 / 0081871(A1) discloses a method comprising chemically mechanically polishing a substrate with an inventive polishing composition comprising a liquid carrier, a cationic polymer, an acid, and abrasive particles treated with an aminosilane compound.

[0017] U.S. Patent Application Publication No. 2014 / 0248823(A1) describes a chemical-mechanical polishing composition containing (a) abrasive particles, (b) a polymer, and (c) water, wherein (i) the polymer has a total charge, (ii) the abrasive particles have a zeta-potential Za measured in the absence of the polymer, and a zeta-potential Zb measured in the presence of the polymer, where Za is a value with the same sign as the total charge of the polymer, and (iii) |Zeta-potential Zb|>|Zeta-potential Za|. The present invention also provides a method for polishing a substrate with the polishing composition.

[0018] The use of polyelectrolytes such as poly(acrylic acid), poly(methacrylic acid), poly(vinylsulfonic acid), poly(acrylic acid-co-maleic acid), poly(vinylamine), poly(ethyleneimine), and poly(4-vinylpyridine) as slurry components to achieve higher levels of planarization has been described in previous patents (U.S. Pat. No. 5,876,490). Other publications have generally reported on "cationic water-soluble polymers" such as polyvinylpyrrolidone, polyallylamine, polyvinylpiperazine, or polylysine and their positive effects in tungsten CMP (U.S. Pat. App. Pub. Nos. 2010 / 0075501 A1 and 2010 / 0252774 A1).

[0019] Generally, the described polyelectrolytes essentially contain nitrogen-containing cations of the ammonium type. The synergistic effects of different cation types in the backbone of imidazolium-type cationic polymers, phosphonium-based polyionic liquids, guanidinium- or triazolium-based polymers, or copolymers have been identified and used in CMP slurries in U.S. Provisional Application Nos. 63 / 191047, filed May 20, 2021; 63 / 209306, filed June 10, 2021; 63 / 251127, filed October 1, 2021; and 63 / 362810, filed April 11, 2022, each of which is incorporated herein by reference in its entirety.

[0020] One of the problems commonly encountered in CMP, especially in metal applications such as tungsten, is dishing of tungsten lines and erosion of metal line arrays. Dishing and erosion are important CMP parameters that define the planarity of the polished wafer. Line dishing typically increases for wider lines. Array erosion typically increases with increasing pattern density.

[0021] Furthermore, metal CMP is based on the Fenton reaction, which converts a hard metal layer into a soft oxide layer that can be easily removed by mechanical polishing. However, these oxidizing conditions can result in corrosion defects that limit overall CMP results.

[0022] Tungsten CMP slurries should be formulated to minimize dishing, erosion, and corrosion to meet specific design goals that are critical to device functionality.

[0023] Finding solutions to control topology defects such as erosion and dishing is important for future CMP requirements. There remains a need for new tungsten CMP slurries that can reduce dishing and erosion while maintaining desirable removal rates during polishing. Summary of the Invention

[0024] The present invention fills this need by providing an intelligently designed tungsten CMP slurry, a system and method for using the CMP slurry, to minimize the noted problems of dishing and erosion in highly selective tungsten slurries while maintaining desirable polishing of metal layers, particularly tungsten films.

[0025] Polymer additives play an important role as dispersants and passivators in slurry development to obtain the desired removal rate, selectivity and degree of defectivity.

[0026] The present invention discloses the synthesis of guanidinium-based polyionic liquids and demonstrates that the use of the synthesized guanidinium-based polyionic liquids in CMP slurries reduces the described problems by tailoring removal rate and selectivity, and by reducing dishing and erosion to control overall topography.

[0027] A guanidinium-based polymer or copolymer is a cationic polymer or copolymer formed by two or more monomers having at least one guanidinium group or having two or more repeat units having at least one guanidinium group.

[0028] Additionally, some specific aspects of the present invention are outlined below. Aspect 1: The guanidinium-based polymer or copolymer has the following structure: [ka] [In the formula, P1 represents a polymerizable group; Sp1 represents a spacer group; preferably, Sp1 has a substituted or unsubstituted aliphatic moiety having single bonds at its two ends; R1 is H or a substituted or unsubstituted aliphatic moiety, and CH2 may be replaced by O, S or N in such a way that the heteroatoms are not linked to each other; preferentially, R1 is H, CH3 or CH2-CH3; R2 is H or a substituted or unsubstituted aliphatic moiety, preferentially R2 is H or CH3; R3 is H or a substituted or unsubstituted aliphatic moiety, and two R3 groups can form a bridge between nitrogen atoms to create a 5-, 6-, or 7-membered ring; preferentially, R3 is H or CH3, or two R3 groups form a bridge between nitrogen atoms to create a 5-membered ring; and X - represents an anionic counterion] The compound is formed by two or more monomers having two or more guanidinium groups, Aspect 2: As the polymerizable group P1, styrene (i.e., vinylbenzene), acrylate or methacrylate, vinyl ether, allyl ether, acrylamide or methacrylamide, ethylene oxide, propylene oxide, maleimide, siloxane, norbornene, a group containing a C=C double bond, and combinations thereof; preferably a group containing a C=C double bond, but not limited thereto, the guanidinium-based polymer or copolymer according to Aspect 1. Aspect 3: The following structure: [Chemical formula] [In the formula, n is an integer, and 1 < n < 4000, 50 < n < 2000, or 75 < n < 1000; R1 is H, or a substituted or unsubstituted aliphatic moiety, and preferably, R1 is H, CH3 or CH2-CH3; R2 is H, or a substituted or unsubstituted aliphatic moiety, and both R2 groups can also form a bridge between the nitrogen atoms to construct a 5-membered ring, 6-membered ring or 7-membered ring; preferably, R2 is H or CH3, or two R2 groups form a bridge between the nitrogen atoms to construct a 5-membered ring; and X - represents an anionic counterion] A guanidinium-based polymer or copolymer containing two or more repeating units having Aspect 4: The anionic counterion X - is selected from the group consisting of halides (F - , Cl - , Br - ​​​​​​​​​​​​​​​​Aspect 5: The guanidinium-based polymer or copolymer of Aspects 1-4, formed by a polymerization method 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), or polycondensation reaction. Embodiment 6: The guanidinium-based polymer or copolymer of embodiments 1-5, wherein the copolymer has block copolymer properties. Aspect 7: The guanidinium-based polymer or copolymer of any one of Aspects 1 to 5, which is poly(vinylbenzyl-N-(bis(dimethylamino)methylene-N-methyl)methanaminium chloride), poly(3-acrylamido-N-(bis(dimethylamino)methylene-N-methylpropan-1-aminium bromide), poly(N-(1,3-dimethylimidazolidin-2-ylidene)-N-methyl-1-(4-vinylphenyl)methanaminium chloride); or poly(1-(bis(dimethylamino)methylene)-3,4-ethylenepyrrolidin-1-ium bromide). Aspect 8: An abrasive material; an activator; an oxidizing agent; an additive comprising a guanidinium-based polymer or copolymer according to any one of aspects 1 to 7; Water, optionally A corrosion inhibitor; a dishing reducing agent; A stabilizer and and a pH adjuster. Aspect 9: A system for chemical mechanical planarization, comprising: a semiconductor substrate having at least one surface containing tungsten; A polishing pad; the chemical mechanical planarization composition of embodiment 8; A system in which at least one surface containing tungsten is in contact with a polishing pad and a chemical mechanical planarization composition. Embodiment 10: A polishing method for chemical mechanical planarization of a semiconductor substrate having at least one surface containing tungsten, comprising: a) contacting at least one surface containing tungsten with a polishing pad; b) delivering a chemical mechanical planarization composition according to embodiment 8; c) polishing at least one surface containing tungsten with a chemical mechanical planarizing composition.

[0029] 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, surface modified inorganic oxide particles, and combinations thereof.

[0030] 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.

[0031] 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.

[0032] Organic polymer particles include, but are not limited to, polystyrene particles, polyurethane particles, polyacrylate particles, or any other organic polymer particles.

[0033] Metal oxide-coated organic polymer particles include, but are not limited to, ceria-coated organic polymer particles and zirconia-coated organic polymer particles.

[0034] Examples of surface-modified inorganic oxide particles include, but are not limited to, SiO2-R-NH2, -SiO-R-SO3M, where R is, for example, (CH2) where n is in the range of 1 to 12. nM may be, for example, sodium, potassium, or ammonium. Examples of such surface-chemically modified silica particles include, but are not limited to, Fuso PL-2C manufactured by Fuso Chemical Co., Ltd.

[0035] The concentration of the abrasive may range from 0.01% to 30% by weight, preferably from about 0.05% to about 20% by weight, more preferably from about 0.01 to about 10% by weight, and most preferably from 0.1% to 2% by weight, where the weight percentages are based on the composition.

[0036] Activators include, but are not limited to, (1) inorganic oxide particles coated with a transition metal, wherein the transition metal is selected from the group consisting of Fe, Cu, Mn, Co, Ce, and combinations thereof; (2) soluble catalysts selected from the group consisting of iron (III) nitrate, ammonium iron (III) oxalate trihydrate, tribasic iron (III) citrate monohydrate, iron (III) acetylacetonate, and ethylenediaminetetraacetic acid, iron (III) sodium salt hydrate; and (3) metal compounds having multiple oxidation states selected from the group consisting of Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V, and combinations thereof.

[0037] The activator ranges from 0.00001% to 5.0% by weight, from 0.0001% to 2.0% by weight, from 0.0005% to 1.0% by weight, or from 0.001% to 0.5% by weight.

[0038] Oxidizing agents include, but are not limited to, peroxy compounds selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, propane peroxoacids, substituted or unsubstituted butane peroxoacids, hydroperoxyacetaldehyde, potassium periodate, and ammonium peroxymonosulfate, and non-peroxy compounds selected from the group consisting of ferric nitrite, KClO4, KBrO4, and KMnO4.

[0039] The oxidizing agent concentration can range from about 0.01% to 30% by weight, with a preferred concentration of oxidizing agent being from about 0.1% to 20% by weight, and a more preferred concentration of oxidizing agent being from about 0.5% to about 10% by weight. The weight percentages are of the composition.

[0040] The overall amount of the additive, including the guanidinium-based polymer or copolymer, ranges from 0.00001% to 1.0%, 0.0001% to 0.5%, 0.0002% to 0.1%, or 0.0005% to 0.05% by weight.

[0041] 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.

[0042] The pH of the slurry is 1-14, preferably 1-7, more preferably 1-6, and most preferably 1.5-4.

[0043] The CMP slurry may further include surfactants, dispersants, chelating agents, film-forming corrosion inhibitors, and biocides.

[0044] Other aspects, features and embodiments of the present invention will become more fully apparent from the following disclosure and appended claims.

[0045] The embodiments of the present invention may be used alone or in combination with each other. DETAILED DESCRIPTION OF THE INVENTION

[0046] The present invention fills this need by providing an intelligently designed tungsten CMP slurry, a system and method for using the CMP slurry, to reduce the noted problems of dishing and erosion in highly selective slurries while maintaining desirable polishing of metal layers, particularly tungsten films.

[0047] More specifically, the present invention discloses the synthesis of guanidinium-based polymers or copolymers and demonstrates the use of the synthesized guanidinium-based polymers or copolymers in CMP slurries to reduce the described problems by tailoring removal rate and selectivity, and by reducing dishing and erosion to control overall topography.

[0048] Highly selective slurries have a large difference in metal removal rate versus dielectric removal rate and are of great interest for future industrial needs. In most cases, the use of these slurries is accompanied by high levels of CMP defects, such as metal dishing or oxide erosion, due to the need for long overpolishing times.

[0049] Furthermore, metal CMP is based on the Fenton reaction, which converts a hard metal layer into a soft oxide layer that can be easily removed by mechanical polishing. However, these oxidizing conditions can result in corrosion defects that limit overall CMP results.

[0050] Topographic defects such as metal dishing or oxide erosion make the performance and selectivity goals of many CMP applications extremely challenging, and pose a major challenge in the development of increasingly smaller integrated circuits.

[0051] Certain water-soluble cationic polymers are key elements in tailored slurry formulations to reduce defects while enabling the desired removal rate and selectivity. These polymer additives play an important role as dispersants and passivators in slurry development to obtain the desired removal rate, selectivity, and degree of defectivity.

[0052] Negatively charged polymers are generally capable of electrostatically interacting with oppositely charged surfaces, such as positively charged tungsten surfaces, and therefore, by using optimized amounts and tailored polymers, the selectivity between metal removal and oxide layer removal can be significantly increased while reducing dishing effects.

[0053] You, K. et al. (ECS Journal of Solid State Science and Technology 2017, 6(12), p. 822) explain that at low pH values ​​below 2.5, the SiO2 layer, a standard oxide material, never becomes partially negatively charged. In other words, to prevent oxide erosion simultaneously with metal dishing, the polymers used require more specific design beyond a purely cationic approach.

[0054] The guanidine or guanidinium group is a unique functional group with unique properties, essentially characterized by its ability to strongly interact with various anionic functional groups by forming ion pairs in combination with strong hydrogen bonds. The positive charge of guanidinium can be evenly distributed among the three nitrogen atoms through resonance. Many important mechanisms of life and biochemistry are based in principle on this special property, as guanidinium functional groups are frequently used by proteins and enzymes to recognize and bind anions. This is taught by Hannon, CL et al. (In Bioorganic Chemistry Frontiers; Dugas, H.; Schmidtchen, FP, Eds.; Springer Berlin Heidelberg: Berlin, Heidelberg, 1993, DOI: 10.1007 / 978-3-642-78110-0_6).

[0055] Among the polymers used in CMP slurries, guanidinium polymers have surprisingly not been described as additives for CMP slurries.

[0056] A guanidinium-based polymer or copolymer is a cationic polymer or copolymer formed by two or more monomers having at least one guanidinium group or having two or more repeat units having at least one guanidinium group. Guanidinium-based polymers or copolymers include homopolymers, random copolymers, and block copolymers.

[0057] Guanidinium-containing polymers are not only characterized by their interaction with metal atoms, but also, due to their cationic nature, can electrostatically interact with some oppositely charged surfaces, which has a positive effect on removal rate, selectivity, and CMP defects.

[0058] Comparative testing of different cationic polyvinylbenzene polymers in this application showed that the dishing and erosion behavior of guanidinium-based polymers was very low, surpassing all other cationic types tested. In short, guanidinium-based polymers may be a new tool in advanced slurry design, expanding the existing toolbox of topography-controlling polymers.

[0059] All references cited in this specification, including publications, patent applications, and patents, are herein incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0060] In the context of describing the present invention (particularly in the context of the claims below), the use of the terms "a," "an," and "the," and similar references, should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise indicated. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended merely to better elucidate the invention and does not impose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention. The use of the term "comprising" in this specification and claims includes the narrower language of "consisting essentially of" and "consisting of."

[0061] Embodiments are described herein, including the best mode known to the inventors for carrying out the invention. Variations of these embodiments may become apparent to those skilled in the art upon reading the foregoing description. The inventors anticipate that skilled artisans will employ such variations as appropriate, and the inventors intend that the invention may be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Furthermore, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or clearly contradicted by context.

[0062] For ease of reference, a "microelectronic device" corresponds to semiconductor substrates, flat panel displays, phase change memory devices, solar panels and other products including solar substrates, photovoltaic devices, and microelectromechanical systems (MEMS) manufactured for use in 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 may be doped or undoped. It should be understood that the term "microelectronic device" is not intended to be limiting in any way and includes any substrate that ultimately becomes a microelectronic device or microelectronic assembly.

[0063] "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.

[0064] As used herein, "about" is intended to correspond to ±5%, preferably ±2% of the stated value.

[0065] In all such compositions where a particular component of a composition is discussed with reference to a weight percent range that includes a lower limit of zero, it will be understood that such component may or may not be present in various particular embodiments of the composition, and that when such component is present, such component may be present in concentrations as low as 0.00001 weight percent, based on the total weight of the composition in which such component is used.

[0066] There are several specific aspects to the present invention.

[0067] One embodiment is for synthesizing a guanidinium-based polymer or copolymer by a polymerization method 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), or polycondensation reactions.

[0068] Another embodiment is a CMP slurry, which includes an abrasive, an oxidizer (i.e., an oxidizer that is not a free radical generator), an activator or catalyst, an additive including a guanidinium-based cationic polymer or copolymer, and water; and optionally, a corrosion inhibitor, a dishing-reducing agent, a stabilizer, and a pH adjuster. The pH of the slurry is 1 to 14, preferably 1 to 7, more preferably 1 to 6, and most preferably 1.5 to 4.

[0069] The CMP slurry may further include surfactants, dispersants, chelating agents, film-forming corrosion inhibitors, biocides, and polishing enhancers.

[0070] Yet another aspect is a system for chemical mechanical planarization, comprising: a semiconductor substrate having at least one surface containing tungsten; A polishing pad; a chemical mechanical planarization composition; A system for chemical mechanical planarization in which at least one surface containing tungsten is in contact with a polishing pad and a chemical mechanical planarization composition.

[0071] Yet another aspect is a polishing method for chemical mechanical planarization of a semiconductor substrate having at least one surface containing tungsten, comprising: contacting at least one surface containing tungsten with a polishing pad; delivering a chemical mechanical planarization composition; polishing at least one surface containing tungsten with a chemical mechanical planarizing composition.

[0072] Abrasive material 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.

[0073] The abrasives used in the CMP slurry may be activator-containing particles (ie, abrasives having an activator coating) or non-activator-containing particles.

[0074] Inorganic oxide particles include, but are not limited to, ceria, silica, alumina, titania, germania, spinel, tungsten oxides or nitrides, zirconia particles, or any of the above doped with one or more other minerals or elements, and any combination thereof. Oxide abrasives can be produced by any of a variety of techniques, including sol-gel, hydrothermal, hydrolysis, plasma, pyrolysis, aerogel, fuming, and precipitation methods, and any combination thereof.

[0075] Precipitated inorganic oxide particles can be obtained by known methods by reacting metal salts with acids or other precipitating agents. Pyrolytic metal oxide and / or metalloid oxide particles can be obtained by hydrolysis of suitable vaporizable starting materials in an oxygen / hydrogen flame. One example is pyrolytic silicon dioxide from silicon tetrachloride. Pyrolytic oxides of aluminum oxide, titanium oxide, zirconium oxide, silicon dioxide, cerium oxide, germanium oxide, and vanadium oxide, as well as chemical and physical mixtures thereof, are suitable.

[0076] 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.

[0077] The metal oxide coated organic polymer particles are selected from the group consisting of ceria coated organic polymer particles and zirconia coated organic polymer particles.

[0078] Organic polymer particles include, but are not limited to, polystyrene particles, polyurethane particles, polyacrylate particles, or any other organic polymer particles.

[0079] Colloidal silica particles and high-purity colloidal silica particles are preferred abrasive particles. The silica may be precipitated silica, fumed silica, pyrogenic silica, silica doped with one or more adjuvants, or any other silica-based compound.

[0080] Colloidal silica particles and high-purity colloidal silica particles used as abrasives also include silica particles that have been surface-chemically modified via chemical coupling reactions, which allow the surface of such silica particles to have different chemical functional groups and to have positive or negative charges under different application pH conditions in the CMP slurry. Examples of such surface-chemically modified silica particles include, but are not limited to, SiO2-R-NH2, -SiO-R-SO3M, where R is, for example, (CH2) where n is in the range of 1 to 12. n M may be, for example, sodium, potassium, or ammonium.

[0081] An example of such surface chemically modified silica particles includes, but is not limited to, Fuso PL-2C manufactured by Fuso Chemical Co., Ltd.

[0082] In alternative embodiments, the silica may be produced by a process selected from the group consisting of, for example, a sol-gel process, a hydrothermal process, a plasma process, a fuming process, a precipitation process, and any combination thereof.

[0083] The abrasive is generally in the form of abrasive particles, typically many abrasive particles, of one material or a combination of different materials. Generally, suitable abrasive particles are approximately spherical and have an effective diameter of about 10 to 700 nm, about 20 to 500 nm, or about 30 to 300 nanometers (nm), although individual particle sizes can vary. Abrasives in the form of agglomerated or weakly agglomerated particles are preferably further processed to form individual abrasive particles.

[0084] The abrasive particles may be purified using a suitable method, such as ion exchange, to remove metal impurities, which may help improve colloidal stability. Alternatively, high purity abrasive particles are used.

[0085] Generally, the above-mentioned abrasives can be used alone or in combination with each other. To obtain superior performance, it may be advantageous to combine two or more abrasive particles having different sizes or different types of abrasives.

[0086] The concentration of the abrasive may range from 0.01% to 30% by weight, preferably from about 0.05% to about 20% by weight, more preferably from about 0.01 to about 10% by weight, and most preferably from 0.1% to 2% by weight, where the weight percentages are based on the composition.

[0087] additives The CMP slurry of the present invention includes an additive that is a guanidinium-based polymer or copolymer.

[0088] The guanidinium-based polymer or copolymer is formed by a polymerization method 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), or polycondensation reaction.

[0089] A guanidinium-based polymer or copolymer is a cationic polymer or copolymer formed by two or more monomers having at least one guanidinium group, the monomers having the following structure: [ka] [In the formula, P1 represents a polymerizable group; Sp1 represents a spacer group; preferably, Sp1 has a substituted or unsubstituted aliphatic moiety having single bonds at its two ends; R1 is H or a substituted or unsubstituted aliphatic moiety, and CH2 may be replaced by O, S or N in such a way that the heteroatoms are not linked to each other; preferentially, R1 is CH3 or CH2-CH3; R2 is H or a substituted or unsubstituted aliphatic moiety, preferentially R2 is H, CH3; or CH2-CH3; R3 is H or a substituted or unsubstituted aliphatic moiety, and two R3 groups can form a bridge between the nitrogen atoms to create a 5-, 6-, or 7-membered ring; Preferably, R3 is H or CH3, or two R3 groups form a bridge between nitrogen atoms to construct a 5-membered ring; and X - represents an anionic counter ion] is included.

[0090] As the polymerizable group P1, styrene (i.e., vinylbenzene), acrylate or methacrylate, vinyl ether, allyl ether, acrylamide or methacrylamide, ethylene oxide, propylene oxide, maleimide, siloxane, norbornene, a group containing a C=C double bond, and combinations thereof; preferably a group containing a C=C double bond, but not limited thereto.

[0091] The anionic counter ion X - includes halides (F - , Cl - , Br - , I - ), BF4 - , PF6 - , carboxylate, malonate, citrate, carbonate, fumarate, MeOSO3 - , MeSO3 - , CF3COO - , CF3SO3 - , nitrate or sulfate, but not limited thereto, and Me is methyl.

[0092] The guanidinium-based polymer or copolymer has the following structure: [[ID=​​​​​​​​​​R2 is H or a substituted or unsubstituted aliphatic moiety, and both R2 groups can form a bridge between the nitrogen atoms to create a 5-, 6-, or 7-membered ring; preferentially, R2 is H or CH3, or two R2 groups form a bridge between the nitrogen atoms to create a 5-membered ring; and X - represents an anionic counterion] The cationic polymer or copolymer has a repeating unit having the formula:

[0093] Anionic counterion X - As for the halides (F - , Cl - , Br - , I - ), BF4 - , PF6 - , carboxylate, malonate, citrate, carbonate, fumarate, MeOSO3 - , MeSO3 - , CF3COO - , CF3SO3 - , nitrate or sulfate.

[0094] The guanidinium-based polymer or copolymer additive has a concentration ranging from about 0.00001% to 1.0%, 0.0001% to 0.5%, 0.0002% to 0.1%, or 0.0005% to 0.05% by weight.

[0095] oxidizing agent The CMP slurry of the present invention includes an oxidizing agent or oxidizer for chemical etching of materials.

[0096] The oxidizer of the CMP slurry is in a fluid composition that is in contact with the substrate and aids in the chemical removal of target materials on the substrate surface. Thus, the oxidizer component is believed to enhance or increase the material removal rate of the composition. Preferably, the amount of oxidizer in the composition is sufficient to assist the chemical removal process, but is as low as possible to minimize similar or related issues, such as handling, environmental concerns, or cost.

[0097] Advantageously, in one embodiment of the present invention, the oxidizing agent is a component that generates free radicals upon exposure to at least one activating agent, which increase the etch rate on at least selected structures. The free radicals described below oxidize most metals, making the surface more susceptible to oxidation from other oxidizing agents. However, because some oxidizing agents do not readily form free radicals upon exposure to an activating agent, and in some embodiments, it is advantageous to have one or more oxidizing agents that provide tailored or preferential etch rates for various combinations of metals that may be found on a substrate, oxidizing agents are listed separately from the "compounds that generate free radicals" discussed below.

[0098] As is known in the art, some oxidizers are more suitable for certain components than others. In some embodiments of the present invention, the selectivity of a CMP system for one metal as opposed to another is maximized, as is known in the art. However, in certain embodiments of the present invention, the combination of oxidizers is selected to provide substantially similar CMP rates (as opposed to simply etch rates) for the combination of conductor and barrier.

[0099] In one embodiment, the oxidizing agent is an inorganic or organic percompound.

[0100] Percompounds are generally defined as compounds containing elements in their highest oxidation state, such as perchloric acid, or compounds containing at least one peroxy group (-OO-), such as peracetic acid and perchromic acid.

[0101] Suitable per-compounds containing at least one peroxy group include, but are not limited to, peracetic acid or its salts, percarbonates, and organic peroxides such as benzoyl peroxide, urea peroxide, and / or di-t-butyl peroxide.

[0102] Suitable per-compounds containing at least one peroxy group include peroxides. As used herein, the term "peroxide" encompasses ROO-R', where R and R' are each independently H, C1-C6 linear or branched alkyl, alkanol, carboxylic acid, ketone (for example), or amine, each of which may be independently substituted with one or more benzyl groups (e.g., benzoyl peroxide), which may themselves be substituted with OH or C1-C5 alkyl, as well as salts and adducts thereof. Thus, the term encompasses common examples such as hydrogen peroxide, peroxyformic acid, peracetic acid, propane peroxoacid, substituted or unsubstituted butane peroxoacid, hydroperoxyacetaldehyde, and the like, and also encompasses common complexes of peroxides, such as urea peroxide.

[0103] Suitable percompounds containing at least one peroxy group include persulfates. As used herein, the term "persulfates" includes monopersulfates, dipersulfates, and their acids, salts, and adducts. Examples include peroxydisulfates, peroxymonosulfates, and / or peroxymonosulfates, Caro's acid, and salts such as potassium peroxymonosulfate, but preferably non-metal salts such as ammonium peroxymonosulfate.

[0104] Suitable per-compounds containing at least one peroxy group include perphosphates, including peroxydiphosphates, as defined above.

[0105] Ozone is also a suitable oxidizing agent, either alone or in combination with one or more other suitable oxidizing agents.

[0106] Suitable per-compounds that do not contain a peroxy group include, but are not limited to, periodic acid and / or any salt of periodate (hereinafter "periodate"), perchloric acid and / or any salt of perchlorate (hereinafter "perchlorate"), perbromic acid and / or any salt of perbromate (hereinafter "perbromate"), and perboric acid and / or any salt of perborate (hereinafter "perbromate").

[0107] Other oxidizing agents are also suitable components of the compositions of the present invention. Iodate is a useful oxidizing agent.

[0108] Two or more oxidizers may be combined to provide synergistic performance benefits.

[0109] In most embodiments of the present invention, the oxidizing agent is selected from the group consisting of peroxy compounds selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, propane peroxoacids, substituted or unsubstituted butane peroxoacids, hydroperoxyacetaldehyde, potassium periodate, and ammonium peroxymonosulfate, and non-peroxy compounds selected from the group consisting of ferric nitrite, KClO, KBrO, and KMnO.

[0110] In some embodiments, the preferred oxidizing agent is hydrogen peroxide.

[0111] The oxidizing agent concentration can range from about 0.01% to 30% by weight, with a preferred concentration of oxidizing agent being from about 0.1% to 20% by weight, and a more preferred concentration of oxidizing agent being from about 0.5% to about 10% by weight. The weight percentages are of the composition.

[0112] activator An activator or catalyst is a material that promotes the formation of free radicals by at least one free radical-producing compound present in the fluid interacting with an oxidizer.

[0113] The activator may be a metal-containing compound, particularly a metal selected from the group consisting of metals known to activate the Fenton reaction process in the presence of an oxidizing agent such as hydrogen peroxide.

[0114] The activator may be a non-metal-containing compound. Iodine is useful, for example, to form free radicals with hydrogen peroxide.

[0115] If the activator is a metal ion or metal-containing compound, the activator is present in a thin layer attached to the surface of a solid in contact with the fluid. If the activator is a non-metal-containing material, the activator can be dissolved in the fluid. The activator is preferably present in an amount sufficient to promote the desired reaction.

[0116] Activators include, but are not limited to, (1) inorganic oxide particles having a transition metal coated thereon, wherein the transition metal is selected from the group consisting of iron, copper, manganese, cobalt, cerium, and combinations thereof; (2) soluble catalysts, including, but not limited to, iron (III) nitrate, ammonium iron (III) oxalate trihydrate, iron (III) citrate tribasic monohydrate, iron (III) acetylacetonate, and ethylenediaminetetraacetic acid, iron (III) sodium salt hydrate, metal compounds having multiple oxidation states selected from the group consisting of Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V, and combinations thereof.

[0117] The amount of activator in the slurry ranges from about 0.00001% to 5% by weight, preferably from about 0.0001% to 2.0% by weight, more preferably from about 0.0005% to 1.0% by weight, and most preferably from 0.001% to 0.5% by weight.

[0118] water The polishing composition is water-based and therefore contains water.In the composition, water functions in various ways, for example, to dissolve one or more solid components of the composition, as a carrier of 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.

[0119] For most applications, the water content will be, for example, from about 10 to about 90% or 90% by weight water. Other preferred embodiments may include from about 30 to about 95% by weight water. Still other preferred embodiments may include from about 50 to about 90% by weight water. Still other preferred embodiments may include water in an amount to achieve the desired weight percentages of the other ingredients.

[0120] Corrosion inhibitor (optional) Corrosion inhibitors for use 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, triazine thiols, triazine dithiols, and triazine trithiols, pyrazoles, imidazoles, isocyanurates such as 1,3,5-tris(2-hydroxyethyl)isocyanurate, and mixtures thereof. Preferred corrosion inhibitors are 1,2,4-triazole, 5-aminotriazole, and 1,3,5-tris(2-hydroxyethyl)isocyanurate.

[0121] 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%.

[0122] dishing reducer (optional) The CMP composition may further comprise a dishing-reducing agent or dishing reducer selected from the group consisting of sarcosinates and related carboxylic acid compounds, hydrocarbon-substituted sarcosinates, amino acids, organic polymers and copolymers with molecules containing ethylene oxide repeat 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 with three or more carbon atoms that form alkylammonium ions, aminoalkyls with three or more carbon atoms, polymeric corrosion inhibitors containing at least one nitrogen-containing heterocycle or tertiary or quaternary nitrogen atom repeat group, polycationic amine compounds, cyclodextrin compounds, polyethyleneimine compounds, glycolic acid, chitosan, sugar alcohols, polysaccharides, alginate compounds, and sulfonic acid polymers. Glycine is a preferred dishing-reducing agent.

[0123] When present, the amount of dishing reducing agent ranges from about 0.001 wt % to 2.0 wt %, preferably 0.005 wt % to 1.5 wt %, and more preferably 0.01 wt % to 1.5 wt %, based on weight per weight of the total CMP composition.

[0124] Stabilizer (optional) The composition may also include one or more of a variety of optional additives. Suitable optional additives include stabilizers. These optional additives are generally used to facilitate or promote stabilization of the composition against settling, agglomeration (including particle precipitation, strong or weak agglomeration, etc.), and decomposition. Stabilizers can be used to extend the working life of oxidizers containing compounds that generate free radicals by isolating activator materials, quenching free radicals, or otherwise stabilizing compounds that form free radicals.

[0125] Several materials are useful for stabilizing hydrogen peroxide. One exception to metal contamination is the presence of selected stabilizing metals, such as tin. In some embodiments of the present invention, tin can be present in small amounts, typically less than about 25 ppm, e.g., about 3 to about 20 ppm. Similarly, zinc is often used as a stabilizer. In some embodiments of the present invention, zinc can be present in small amounts, typically less than about 20 ppm, e.g., about 1 to about 20 ppm. In another preferred embodiment, the fluid composition contacting the substrate has less than 500 ppm, e.g., less than 100 ppm, of dissolved metals, excluding tin and zinc, having multiple oxidation states. In the most preferred commercial embodiment of the present invention, the fluid composition contacting the substrate has less than 9 ppm of dissolved metals, excluding tin and zinc, having multiple oxidation states, e.g., less than 2 ppm of dissolved metals, excluding tin and zinc. In some preferred embodiments of the present invention, the fluid composition contacting the substrate has less than 50 ppm, preferably less than 20 ppm, and more preferably less than 10 ppm of dissolved total metals, excluding tin and zinc.

[0126] Since metals in solution are generally not recommended, non-metal-containing oxidizers, which are typically present in salt form, e.g., persulfates, are preferably in acid form and / or ammonium salt form, e.g., ammonium persulfate.

[0127] Other stabilizers include free radical quenchers. As mentioned above, these attenuate the effects of generated free radicals. Therefore, if present, they are preferably present in small amounts. Most antioxidants, such as vitamin B, vitamin C, and citric acid, are free radical quenchers. While most organic acids are free radical quenchers, three that are effective and have other beneficial stabilizing properties are phosphonic acid, the binder oxalic acid, and the non-radical sequestering agent gallic acid.

[0128] Additionally, carbonates and phosphates are believed to bind to the activator and prevent fluid access. Carbonates are particularly useful because they can be used to stabilize the slurry, although small amounts of acid can quickly remove the stabilizing ions. A useful stabilizer for absorbed activators may be a film-forming agent that forms a film on the silica particles.

[0129] Suitable stabilizers include organic acids such as adipic acid, phthalic acid, citric acid, malonic acid, orthophthalic acid, and phosphoric acid, substituted or unsubstituted phosphonic acids, i.e., phosphonate compounds, nitriles, and other ligands, such as those that bind to activator materials and thereby reduce reactions that decompose oxidizers, as well as any combination of the aforementioned agents. As used herein, the term "acid stabilizing agent" refers to both the acid stabilizer and its conjugate base. That is, various acid stabilizers can also be used in their conjugated form. By way of example, for the acid stabilizers mentioned above, the adipic acid stabilizer herein includes adipic acid and / or its conjugate base, and the carboxylic acid stabilizer includes a carboxylic acid and / or its conjugate base, carboxylate, etc. Suitable stabilizers, used alone or in combination with one or more other stabilizers, reduce the rate at which an oxidizer, such as hydrogen peroxide, decomposes when incorporated into a CMP slurry.

[0130] On the other hand, the presence of a stabilizer in the composition may impair the effectiveness of the activator. The amount should be adjusted to meet the required stability while minimizing adverse effects 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 required amount will vary depending on the specific additive selected and the specific configuration of the CMP composition, such as the surface properties of the abrasive component. If too little additive is used, the additive will have little or no effect on the stability of the composition. On the other hand, if too much additive is used, the additive may contribute to the formation of undesirable bubbles and / or flocculants in the composition.

[0131] Generally, suitable amounts of these stabilizers range from about 0.0001 to 5% by weight, preferably from about 0.00025 to 2% by weight, and more preferably from about 0.0005 to about 1% by weight of the composition. The stabilizer may be added directly to the composition or may be applied to the surface of the abrasive component of the composition.

[0132] pH adjuster (optional) The compositions disclosed herein contain a pH adjuster. The pH adjuster is typically used in the compositions disclosed herein to increase or decrease the pH of the polishing composition. The pH adjuster can be used, as needed, to improve the stability of the polishing composition, adjust the ionic strength of the polishing composition, and improve safety in handling and use.

[0133] 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.

[0134] When used, the amount of the pH adjuster is preferably in the range of about 0.01 wt % to about 5.0 wt %, based on the total weight of the polishing composition, with a preferred range being about 0.01 wt % to about 1 wt %, or about 0.05 wt % to about 0.15 wt %.

[0135] The pH of the slurry is 1-14, preferably 1-7, more preferably 1-6, and most preferably 1.5-4.

[0136] Surfactant (optional) The compositions disclosed herein optionally contain a surfactant, which in part protects the wafer surface during and after polishing, helping to reduce defects on the wafer surface.Surfactants can also be used to control the removal rate of some films used in polishing, such as low-K dielectrics.Suitable surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof.

[0137] Nonionic surfactants may be selected from a range of chemical types including, but not limited to, long chain alcohols, ethoxylated alcohols, ethoxylated acetylenic diol 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 sorbitone alkyl esters, sorbitone alkyl esters, cocamide monoethanolamine, cocamide diethanolamine dodecyldimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amine, fluorosurfactants.

[0138] The molecular weight of surfactants can range from a few hundred to over a million. The viscosity of these materials also has a very wide distribution.

[0139] Anionic surfactants include, but are not limited to, alkyl carboxylates, alkyl polyacrylates, alkyl sulfates, alkyl phosphates, alkyl bicarboxylates, alkyl bisulfates, alkyl biphosphates, such as alkoxy carboxylates, alkoxy sulfates, alkoxy phosphates, alkoxy bicarboxylates, alkoxy bisulfates, alkoxy biphosphates, such as substituted aryl carboxylates, substituted aryl sulfates, substituted aryl phosphates, substituted aryl bicarboxylates, substituted aryl bisulfates, and substituted aryl biphosphates, with suitable hydrophobic tails. Counterions of these surfactants include, but are not limited to, potassium ions, ammonium ions, and other cations. The molecular weights of these anionic surface wetting agents range from several hundred to several hundred thousand.

[0140] Cationic surfactants have a net positive charge on the main part of the molecular backbone and are typically halides of molecules containing a hydrophobic chain and a cationic charge center, such as amine, quaternary ammonium, benzalkonium, and alkylpyridinium ions.

[0141] In another embodiment, the surfactant may be an amphoteric surfactant, which has both positive (cationic) and negative (anionic) charges on the main molecular chain and their corresponding counterions. The cationic portion is based on a primary, secondary, or tertiary amine or a quaternary ammonium cation. The anionic portion may be more variable and may include a sulfonate, as in sultaine CHAPS (3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate) and cocamidopropyl hydroxysultaine. Betaines, such as cocamidopropyl betaine, have a carboxylate with ammonium. Some amphoteric surfactants may have a phosphate anion with an amine or ammonium, such as the phospholipids phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelin.

[0142] Examples of surfactants include, but are not limited to, sodium dodecyl sulfate, sodium lauryl sulfate, ammonium dodecyl sulfate, secondary alkane sulfonates, alcohol ethoxylates, acetylenic surfactants, and any combination thereof. Examples of suitable commercially available surfactants include the TRITON®, Tergitol™, and DOWFAX™ families of surfactants manufactured by Dow Chemicals, as well as various surfactants in the SURFYNOL™, DYNOL™, Zetasperse™, Nonidet™, and Tomadol™ surfactant families manufactured by Air Products and Chemicals. Suitable surfactants among surfactants can also include polymers containing ethylene oxide (EO) and propylene oxide (PO) groups. An example of an EO-PO polymer is Tetronic™ 90R4 manufactured by BASF Chemicals.

[0143] When used, the amount of surfactant typically ranges from 0.0001% to about 1.0% by weight, based on the total weight of the barrier CMP composition. When used, the preferred range is from about 0.010% to about 0.1% by weight.

[0144] Chelating agent (optional) Chelating agents may optionally be used in the compositions disclosed herein to enhance the affinity of the chelating ligand for metal cations. Chelating agents may also be used to prevent the accumulation of metal ions on the pad, which can cause pad contamination and instability in removal rate. Suitable chelating agents include, for example, amine compounds such as ethylenediamine, ethylenediaminetetraacetic acid (EDTA), aminopolycarboxylic acids such as nitrilotriacetic acid (NTA), benzenesulfonic acid, 4-tolylsulfonic acid, 2,Aromatic acids such as 4-diaminobenzosulfonic acid, 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, for example, glycine, serine, proline, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan, valine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, ornithine, selenium, tein, tyrosine, sarcosine, vicine, tricine, aceglutamide, n-acetylaspartic acid, acetylcarnitine, acetylcysteine, n-acetylglutamic acid, acetylleucine, acivicin, s-adenosyl-l-homocysteine, agaritine, alanosine, aminohippuric acid, l-arginine ethyl ester, aspartame, aspartylglucosamine, benzylmercaptouric acid, biocytin, brivanib alaninate, carbocysteine, n(6)-carboxymethyllysine, carbocysteine Glumic acid, cilastatin, cithiolone, coprine, dibromotyrosine, dihydroxyphenylglycine, eflornithine, fenclonine, 4-fluoro-l-threonine, n-formylmethionine, gamma-l-glutamyl-l-cysteine, 4-(gamma-glutamylamino)butanoic acid, glutaurine, glycocyamine, hadacidin, hepapressin, lisinopril, lymecycline, n-methyl-d-aspartic acid, n-methyl-l-glutamic acid, milacemide, nitrosoproline, nocardicin A, Examples of anti-inflammatory drugs include, but are not limited to, paraffin, octopine, ombrulin, opine, orthanilic acid, oxaceprol, polylysine, remacemide, salicylic acid, silk amino acids, stampeidin, tabtoxin, tetrazolylglycine, thiorphan, timectacin, tiopronin, tryptophan tryptophylquinone, valacyclovir, valganciclovir, phosphonic acids and derivatives thereof, such as octylphosphonic acid, aminobenzylphosphonic acid, and combinations thereof and salts thereof.

[0145] For example, a chelating agent may be used where necessary to chemically bond copper and tantalum cations to facilitate dissolution of the copper and tantalum oxides to obtain a desired removal rate of the copper lines, vias, or trenches and barrier layers or films.

[0146] If used, the amount of chelating agent preferably ranges from about 0.01% to about 3.0% by weight, more preferably from about 0.4% to about 1.5% by weight, based on the total weight of the composition.

[0147] Biocide (optional) The CMP formulations disclosed herein may also contain additives for controlling biological growth, such as biocides. Some additives for controlling 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 (with alkyl chains ranging from 1 to about 20 carbon atoms), sodium chlorite, sodium hypochlorite, isothiazolinone compounds such as methylisothiazolinone, methylchloroisothiazolinone, and benzisothiazolinone. Some commercially available preservatives include the KATHON™ and NEOLENE™ product families from Dow Chemicals and the Preventol™ family from Lanxess.

[0148] Preferred biocides are isothiozilone compounds such as methylisothiazolinone, methylchloroisothiazolinone and benzisothiazolinone.

[0149] The CMP polishing composition optionally contains a biocide in the range of 0.0001% to 0.10% by weight, preferably 0.0001% to 0.005% by weight, and more preferably 0.0002% to 0.0025% by weight, to prevent bacterial and fungal growth during storage.

[0150] The compositions disclosed herein may be prepared in a concentrated form and then diluted with DI water at the time of use. For example, other components, such as an oxidizer, may be set aside in the form of a concentrate and added at the time of use to minimize incompatibility between components in the form of a concentrate. The compositions disclosed herein may be prepared with two or more components that can be mixed before use. [Example]

[0151] General Experimental Procedures All percentages are by weight unless otherwise indicated.

[0152] Part I. Synthesis of guanidinium-based polymers and copolymers All reagents and solvents were purchased from Sigma-Aldrich (Merck) of the highest commercial grade and were used as received unless otherwise stated.

[0153] Characterization methods

[0154] 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 calibrated to the internal standard Si(OMe)4 (0.00 ppm).

[0155] The polymers were analyzed by size exclusion chromatography (SEC) in HO / MeOH / EtOAc (54 / 23 / 23, v / v / v) containing 10 mM sodium acetate (flow rate: 0.5 mL / min) performed at 40 °C. Measurements were performed on an Agilent 1260 HPLC equipped with a column set consisting of a PSS Novema precolumn and a PSS Novema MAX ultraheight column. Samples were dissolved at 50 °C in an eluent containing 0.1% ethylene glycol as an internal standard. The average molar mass of the polymer was derived from the refractive index signal based on a poly(2-vinylpyridine) calibration curve.

[0156] Example 1 Synthesis of poly(vinylbenzyl-N-(bis(dimethylamino)methylene-N-methyl)methanaminium chloride): [ka] 1. Monomer synthesis (1) Synthesis of 1,1,2,3,3-pentamethylguanidine [ka]

[0157] Tetramethylurea (CAS: 632-22-4, 4.6 g, 40 mmol) was dissolved in 50 mL of dichloroethane. Oxalyl chloride (CAS: 79-37-8, 8.2 g, 64.8 mmol) was added at room temperature, and the mixture was heated at 60 °C for 2 h. After removing the solvent, the remaining yellow solid was dissolved in 20 mL of dry ethanol, and methylamine solution (CAS: 74-89-5, 33 wt % in absolute ethanol, 33 g, 355 mmol) was added dropwise at 0 °C. The reaction mixture was allowed to warm slowly to room temperature and then refluxed for 4 h. The solvent was evaporated under vacuum, and the residue was treated with 30% aqueous NaOH. The organic layer was extracted with methyl tert-butyl ether (MTBE), dried over anhydrous magnesium sulfate, filtered, and evaporated to give 4.6 g (89%) of a pale yellow oil.

[0158] 1H NMR (500MHz, CDCl3) δ: 2.89 (s, 3H), 2.71 (s, 6H), 2.59 (s, 6H) ppm. (2) Synthesis of N-(bis(dimethylamino)methylene)-N-methyl-1-(4-vinylphenyl)-methanaminium chloride [ka]

[0159] 4-Vinylbenzyl chloride (CAS: 1592-20-7, 4.5 g, 29.5 mmol) was dissolved in 50 mL of acetonitrile. 1,1,2,3,3-Pentamethylguanidine (4.2 g, 32.3 mmol) was added, and the reaction mixture was stirred under reflux for 18 h. The product was precipitated by adding THF to the cooled solution. The solid was filtered, washed twice with THF, and dried under vacuum to give a white solid (7.4 g, 89% yield).

[0160] 1 H NMR(500MHz,DMSO-d6):δ=7.56-7.46(m,2H),7.39-7.28(m,2H),6.76(dd,J=17.7,10.9Hz,1H),5.87(dd,J=17.6,1.0Hz,1H),5.3 0(dd,J=11.0,0.9Hz,1H),4.51(d,J=13.9Hz,1H),4.22(d,J=13.9Hz,1H),3.01(s,3H),2.91(s,6H),2.77(s,3H),2.70(s,3H)ppm. 2. Polymerization: [ka]

[0161] A Schlenk flask was charged with guanidinium-containing styrene (6 g, 21.3 mmol), AIBN (CAS: 78-67-1, 3.7 mg, 0.023 mmol), and 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT, CAS: 461642-78-4, 26 mg, 0.07 mmol). 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, the 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 under vacuum to give 5.5 g of a yellow solid (92% yield).

[0162] 1 H NMR (500 MHz, DMSO-d6) δ: 7.09 (broad s), 6.33 (broad s), 4.33 (broad s), 2.94 (broad s), 2.51 (broad s), 1.30 (broad s) ppm.

[0163] SEC:Mn:22.6kDa;Mw:44.6kDa;PDI:2.0

[0164] Example 2 Synthesis of ammonium-based materials (conventional technology)

[0165] Poly(tributyl-(4-vinylbenzyl)ammonium chloride) was synthesized using the method described in Biomacromolecules (2012), 13(1), 231-238. [ka]

[0166] 1 H NMR (500 MHz, methanol-d₄) δ: 7.32 (broad s), 6.64 (broad s), 4.62 (broad s), 3.21 (broad s), 1.81 (broad s), 1.40 (broad s), 1.08–1.00 (broad m) ppm.

[0167] SEC:Mn:36kDa;Mw:162kDa;PDI:4.5

[0168] Example 3 Synthesis of phosphonium-based materials (prior art)

[0169] Polytributyl(4-vinylbenzyl)phosphonium chloride was synthesized using the method described in U.S. Provisional Application No. 63 / 209306, filed June 10, 2021. [ka]

[0170] 1 H NMR (500 MHz, methanol-d₄) δ: 7.29 (broad s), 6.54 (broad s), 4.04 (broad s), 2.32 (broad s), 1.49 (broad s), 0.96 (broad s) ppm.

[0171] SEC:Mn:90kDa;Mw:352kDa;PDI:3.9

[0172] Example 4 Synthesis of imidazolium-based materials (conventional technology)

[0173] Poly(vinylbenzyl 1-butyl-1H-imidazol-3-ium) chloride was synthesized by using the method described in U.S. Provisional Application No. 63 / 191047, filed May 20, 2021. [ka]

[0174] 1H NMR (500 MHz, methanol-d₄) δ: 9.52 (broad s), 7.70 (broad s), 7.32 (broad s), 6.42 (broad s), 5.52 (broad s), 4.29 (broad s), 2.04–1.71 (broad m), 1.37 (broad s), 0.97 (broad s) ppm.

[0175] SEC:Mn:35kDa;Mw:106kDa;PDI:3.0

[0176] Example 5 Synthesis of poly(3-acrylamide-N-(bis(dimethylamino)methylene-N-methylpropan-1-aminium bromide): [ka] 1. Monomer synthesis (1) Synthesis of N-(3-bromopropyl)-2-propenamide [ka]

[0177] 3-Bromopropylamine hydrobromide (CAS: 5003-71-4, 9.9 g, 45 mmol) was dissolved in 150 mL of chloroform and mixed with triethylamine (TEA, CAS: 121-44-8, 14 mL, 100 mmol) and 4-(dimethylamino)pyridine (DMAP, CAS: 1122-58-3, 288 mg, 2.3 mmol). The solution was cooled to 0 °C, and acryloyl chloride (CAS: 814-68-6, 4.2 mL, 50 mmol) was added dropwise. The mixture was stirred at room temperature for 4 hours, washed with saturated NaHCO3 (2 x 100 mL) and water (2 x 100 mL), dried over MgSO4, filtered, and after addition of 2,6-di-tert-butyl-4-methylphenol (BHT, CAS: 128-37-0, 6.3 mg) as a stabilizer, the solvent was removed (6.45 g, 75% brown oil). 1H NMR(500MHz, CDCl3)δ:6.30(d,J=16.8Hz,1H),6.15(d,J=10.0Hz,1H),6.07(s ,1H),6.66(dd,J=16.8,10.0Hz,1H),3.51-3.41(m,4H),2.17-2.09(m,2H)ppm. (2) Synthesis of 3-acrylamido-N-(bis(dimethylamino)methylene)-N-methylpropan-1-aminium bromide [ka]

[0178] Dissolve N-(3-bromopropyl)-2-propenamide (CAS: 108595-90-0, 5 g, 26 mmol) in 50 mL of acetonitrile. Add 1,1,2,3,3-pentamethylguanidine (3.7 g, 28.5 mmol) and stir the reaction mixture at room temperature overnight. Precipitate the product by adding THF to the solution. Filter the solid, wash it twice with THF, and dry it under vacuum to obtain a yellow solid (5.7 g, 68% yield). 2. Polymerization: [ka]

[0179] A Schlenk flask was charged with guanidinium-containing acrylamide (5 g, 15.6 mmol) and AIBN (CAS: 78-67-1, 3.7 mg, 0.023 mmol). The mixture was dissolved in acetonitrile / water (30 mL, 1:1 v / v), purged with Ar for 30 minutes, and heated at 70 °C for 18 hours. The solution was cooled to room temperature, the 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 under vacuum to give 4.8 g of a yellow oil (96% yield).

[0180] Example 6 Synthesis of poly(N-(1,3-dimethylimidazolidin-2-ylidene)-N-methyl-1-(4-vinylphenyl)methanaminium chloride) [ka] 1. Monomer synthesis (1) Synthesis of N-1,3-trimethylimidazolidin-2-imine [ka]

[0181] 1,3-Dimethyl-2-imidazolidinone (CAS: 80-73-9, 4.6 g, 40 mmol) was dissolved in 50 mL of dichloroethane. Oxalyl chloride (CAS: 79-37-8, 8.2 g, 64.8 mmol) was added at room temperature, and the solution was heated at 60 °C for 2 h. After removing the solvent, the remaining yellow solid was dissolved in 20 mL of dry ethanol, and methylamine solution (CAS: 74-89-5, 33 wt% in absolute ethanol, 33 g, 355 mmol) was added dropwise at 0 °C. The reaction mixture was allowed to warm slowly to room temperature and then refluxed for 4 h. The solvent was evaporated under vacuum, and the residue was treated with 30% aqueous NaOH. The organic layer was extracted with MTBE, dried over anhydrous magnesium sulfate, filtered, and evaporated to give 4.6 g (90%) of a pale yellow oil. (2) Synthesis of N-(1,3-dimethylimidazolidin-2-ylidene)-N-methyl-1-(4-vinylphenyl)methanaminium chloride [ka]

[0182] Dissolve 4-vinylbenzyl chloride (CAS: 1592-20-7, 4.5 g, 29.5 mmol) in 50 mL of acetonitrile. Add N-1,3-trimethylimidazolidin-2-imine (4.1 g, 32.3 mmol) and stir the reaction mixture under reflux for 18 h. Precipitate the product by adding THF to the cooled solution. Filter the solid, wash it twice with THF, and dry it under vacuum to obtain a white solid (5.8 g, 70% yield). 2. Polymerization: [ka]

[0183] A Schlenk flask was charged with guanidinium-containing styrene (6 g, 21.3 mmol), AIBN (CAS: 78-67-1, 3.7 mg, 0.023 mmol), and 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT, CAS: 461642-78-4, 26 mg, 0.07 mmol). The mixture was dissolved in acetonitrile / water (50 mL, 1:1 v / v) and purged with Ar for 30 min. The mixture was then heated at 65 °C for 18 h. The solution was cooled to room temperature, the acetonitrile was removed, and the residue was dissolved in 10 mL of dichloromethane. Finally, 100 mL of THF was added to precipitate the polymer, which was washed twice with THF and dried under vacuum to obtain 5.5 g of a yellow solid (92% yield).

[0184] Example 7 Synthesis of poly(1-(bis(dimethylamino)methylene)-3,4-ethylenepyrrolidin-1-ium bromide) [ka] 1. Monomer synthesis (1) Synthesis of 2-allyl-1,1,3,3-tetramethylguanidine [ka]

[0185] Tetramethylurea (CAS: 632-22-4, 4.6 g, 40 mmol) is dissolved in 50 mL of dichloroethane. Oxalyl chloride (CAS: 79-37-8, 8.2 g, 64.8 mmol) is added at room temperature, and the solution is heated at 60 °C for 2 h. After removing the solvent, the remaining yellow solid is dissolved in 20 mL of dry ethanol, and allylamine (CAS: 107-11-9, 20 g, 355 mmol) is added dropwise at 0 °C. The reaction mixture is slowly warmed to room temperature and then refluxed for 4 h. The solvent is evaporated under vacuum, and the residue is treated with 30% aqueous NaOH. The organic layer is extracted with MTBE, dried over anhydrous magnesium sulfate, filtered, and evaporated to give 5 g (80.6%) of a pale yellow oil. (2) Synthesis of N-(allyl-N-(bis(dimethylamino)methylene)prop-2-en-1-aminium bromide [ka] Dissolve allyl bromide (CAS: 106-95-6, 3.6 g, 29.5 mmol) in 50 mL of acetonitrile. Add 2-allyl-1,1,3,3-tetramethylguanidine (5.0 g, 32.3 mmol) and stir the reaction mixture at room temperature for 18 h. Precipitate the product by adding THF to the solution. Filter the solid, wash it twice with THF, and dry it under vacuum to obtain a white solid (7.4 g, 90% yield). 2. Polymerization: [ka]

[0186] A Schlenk flask is charged with N-(allyl-N-(bis(dimethylamino)methylene)prop-2-en-1-aminium bromide (5.9 g, 21.3 mmol), AIBN (CAS: 78-67-1, 3.7 mg, 0.023 mmol), and 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT, CAS: 461642-78-4, 26 mg, 0.07 mmol). The mixture is dissolved in acetonitrile / water (50 mL, 1:1 v / v) and purged with Ar for 30 min, then heated at 65 °C for 18 h. The solution is cooled to room temperature, the acetonitrile is removed, and the residue is dissolved in 10 mL of dichloromethane. Finally, 100 mL of THF is added to precipitate the polymer, which is washed twice with THF and dried under vacuum to give 4.5 g of a yellow oil (76% yield).

[0187] Part II CMP Experiments The polishing compositions and associated methods described herein are effective for CMP of a wide variety of substrates, including most substrates, and are particularly useful for polishing tungsten substrates.

[0188] The polishing composition uses the guanidinium-based polymer or copolymer synthesized in Part I.

[0189] In the examples below, CMP experiments were performed using the procedures and experimental conditions set out below. Parameters: Å: Angstrom - unit of length BP: Back pressure, unit is psi CMP: chemical mechanical planarization = chemical mechanical polishing CS: Carrier Speed DF: Downforce: Pressure applied during CMP, unit is psi min:minutes mL: milliliter mV: millivolt psi: pounds per square inch PS: Polishing tool platen rotation speed, in rpm (revolutions per minute) SF: flow rate of polishing composition, ml / min Silicon oxide films by chemical vapor deposition (CVD) using TEOS: tetraethyl orthosilicate as a precursor Wt%: Weight percentage (of listed ingredient) Removal rate (RR) = (film thickness before polishing - film thickness after polishing) / polishing time Removal rate and selectivity Tungsten removal rate: Tungsten removal rate measured at 2.5 psi down pressure on the CMP tool TEOS removal rate: TEOS removal rate measured at a given down pressure. The down pressure of the CMP tool was 2.5 psi. SiN removal rate: SiN removal rate measured at a given down pressure. The down pressure of the CMP tool was 2.5 psi. TiN removal rate: TiN removal rate measured at a given down pressure. The down pressure of the CMP tool was 2.5 psi.

[0190] The CMP tool used in the examples was an AMAT 200 mm Mirra® 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 tests.

[0191] 200 mm diameter silicon wafers coated with tungsten, TEOS, SiN, or tungsten-containing SKW patterned structures were obtained from SKW Associate, Inc., 2920 Scott Blvd., Santa Clara, CA 95054. The polishing time for blanket films was 1 minute. Tungsten removal rate was measured using a sheet resistance measurement technique. TEOS removal was measured using an optical technique. The patterned wafers were polished for a predetermined time based on eddy current technology on an Ebara polisher. The polishing time for patterned wafers was 15 seconds past the endpoint identified by eddy current endpoint technology. The patterned wafers were analyzed using a KLA Tencor P15 Profiler (large feature size) or an AFM tool (small feature size).

[0192] Polishing was carried out using a table speed of 111 RPM, a carrier speed of 113 RPM, a slurry flow rate of 200 ml / min, and a downforce of 2.5 psi.

[0193] In the polishing process, a substrate (e.g., a blanket W or patterned W wafer) was placed face down on a polishing pad fixedly mounted on the rotatable platen of a CMP polisher. In this way, the substrate to be polished and planarized was placed in direct contact with the polishing pad. A wafer carrier system or polishing head was used to hold the substrate in a fixed position and apply downward pressure against the backside of the substrate during the CMP process, rotating the platen and substrate. A polishing composition (slurry) was applied (usually continuously) onto the pad during the CMP process to effectively remove material and planarize the substrate.

[0194] PL-2C silica abrasive was purchased from Fuso Chemical Company (Ogura Bldg. 6-6, Nihonbashi-kobuna-cho, Chuo-ku, Tokyo, Japan 103-0024). All reagents and solvents were purchased from Sigma-Aldrich (Merck) of the highest commercial grade and used as received unless otherwise stated.

[0195] In the following working examples, a base CMP slurry was made with 0.01 wt. % ferric nitrate (iron(III) nitrate), 0.08 wt. % malonic acid (a stabilizer), 2.0 wt. % hydrogen peroxide, 0.1 wt. % glycine, and 0.25 wt. % Fuso PL-2C silica particles in water adjusted to a pH of 2.3 with nitric acid.

[0196] The effect of guanidinium-based polymers on tungsten removal rate, erosion, and dishing was examined.

[0197] Example 1 A working CMP slurry was made by adding the guanidinium-based polymers and copolymers described in Part I to a base CMP slurry.

[0198] The removal rates of tungsten, TEOS, and SiN using a guanidinium-based polymer (Example 1) were tested against the base slurry without added polymer and other conventional cationic polyelectrolytes (Examples 2-4).

[0199] The results are shown in Table 1. [Table 1]

[0200] Compared to the base slurry, all examples containing polycationic polymer under the conditions described provide improved selectivity between the removal rates of tungsten versus TEOS and / or tungsten versus SiN.

[0201] After the patterned wafer polishing endpoint was detected by using eddy current measurements, the wafer was polished for an additional 15 seconds of overpolish (OP) time. Tungsten dishing was tested under the same conditions as tested on the base slurry, namely, on different arrays, including a 50 × 50 micron array (dielectric line width / tungsten line width / trench (in microns) separated by a spacer) (50 / 50 μm), a 1 × 1 micron (1 / 1 μm), a 0.5 × 0.5 micron (0.5 / 0.5 μm), a 0.25 × 0.25 micron (0.25 / 0.25 μm), and a 0.18 × 0.18 micron array (0.18 / 0.18 μm). (W line dishing data is shown in Table 2; the base slurry values ​​are the average of eight different measurements.) [Table 2]

[0202] The dishing of the lines typically increases for wider lines. A negative value of W-line dishing essentially means that no W-line dishing was observed (W-line protrusion).

[0203] In a typical tungsten CMP process, tungsten dishing in wider line features is desired to be less than 1500 angstroms (Å).

[0204] The various formulations were tested for erosion at 20% overpolish under the same conditions as tested for the base slurry: i.e., on 7 / 3 μm, 1 / 1 μm, 0.5 / 0.5 μm, 0.25 / 0.25 μm, and 0.18 / 0.18 μm arrays (Table 3). [Table 3]

[0205] Erosion of the array typically increases with increasing pattern density. Negative values ​​for erosion represent protrusion. Essentially no erosion was observed.

[0206] In a typical tungsten CMP process, it is desirable to have erosion in high density features, such as 70% and 90% density <1000 Angstroms.

[0207] As shown in Tables 2 and 3, the working CMP slurries containing small amounts (approximately 15 ppm) of the synthesized guanidinium-based polymers and copolymers exhibited high tungsten removal rates, and as the concentration increased, the tungsten removal effect was suppressed.

[0208] As can be seen from the results shown in Tables 2 and 3, respectively, the use of guanidinium-based polymers can reduce both erosion and dishing (high-density features), whereas other cationic counterparts did not exhibit this beneficial behavior. In summary, all cationic polymers used significantly increase the selectivity of the corresponding slurries, but only the guanidinium-based materials additionally exhibit a beneficial impact on erosion and dishing effects.

[0209] While the principles of the present invention have been described above in connection with preferred embodiments, it is to be clearly understood that this description is made by way of example only and is not intended to limit the scope of the invention. Rather, the detailed description of the preferred exemplary embodiments will provide those skilled in the art with an enabling description for practicing the preferred exemplary embodiments of the invention. Various changes may be made in the function and arrangement of elements without departing from the spirit and scope of the invention, as set forth in the appended claims.

Claims

1. structure: 【Chemistry 1】 [In the formula, P １ represents a polymerizable group; Sp １ represents a spacer group; preferably, Sp １ has a substituted or unsubstituted aliphatic moiety with single bonds at its two termini; R １ is H or a substituted or unsubstituted aliphatic moiety, CH ２ may be replaced by O, S or N in such a way that the heteroatoms are not linked to each other; preferably, R １ is CH ３ or CH ２ -CH ３ and R ２ is H or a substituted or unsubstituted aliphatic moiety; preferably, R ２ is H, CH ３ , or CH ２ -CH ３ and R ３ is H or a substituted or unsubstituted aliphatic moiety; two R ３ The group can form a bridge between nitrogen atoms to create a 5-, 6-, or 7-membered ring; Preferably, R ３ is H, CH ３ or two R ３ The group forms a bridge between the nitrogen atoms to create a five-membered ring; and X － represents an anionic counterion] 1. A guanidinium-based polymer or copolymer comprising two or more monomers containing at least one guanidinium group having the formula:

2. The polymerizable group P １ is selected from the group consisting of styrene (i.e., vinylbenzene), acrylate or methacrylate, vinyl ether, allyl ether, acrylamide or methacrylamide, ethylene oxide, propylene oxide, maleimide, siloxane, norbornene, a group containing a C═C double bond, and combinations thereof; preferably, the polymerizable group P １ 2. The guanidinium-based polymer or copolymer of claim 1, wherein is a group containing a C=C double bond.

3. Structure (A): 【Chemistry 2】 [In the formula, n represents the number of repeating units, and is 1<n<4000, 50<n<1500, or 75<n<1000; R １ is H or a substituted or unsubstituted aliphatic moiety, preferably R １ is H, CH ３ or CH ２ -CH ３ and R ２ is H or a substituted or unsubstituted aliphatic moiety; two R ２ The group can form a bridge between nitrogen atoms to create a 5-, 6-, or 7-membered ring; Preferably, R ３ is H, CH ３ or two R ２ The group forms a bridge between the nitrogen atoms to complete a five-membered ring; X － represents an anionic counterion] A guanidinium-based polymer or copolymer comprising two or more repeat units having the formula:

4. the anionic counterion X － However, halide (F － , Cl － ,Br － , or I － ), B.F. ４ － , P.F. ６ － , carboxylate, malonate, citrate, carbonate, fumarate, MeOSO ３ － , MeSO ３ － , C.F. ３ COO － , C.F. ３ SO ３ － 4. The guanidinium-based polymer or copolymer of any one of claims 1 to 3, wherein Me is selected from the group consisting of nitrate and sulfate, and Me is methyl.

5. 5. The guanidinium-based polymer or copolymer of any one of claims 1 to 4, formed by a polymerization method 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 reactions.

6. The guanidinium-based polymer or copolymer of any one of claims 1 to 5, wherein the copolymer has block copolymer properties.

7. The guanidinium-based polymer or copolymer according to any one of claims 1 to 6, wherein the guanidinium-based polymer is poly(vinylbenzyl-N-(bis(dimethylamino)methylene-N-methyl)methanaminium chloride), poly(3-acrylamide-N-(bis(dimethylamino)methylene-N-methylpropan-1-aminium bromide); poly(N-(1,3-dimethylimidazolidin-2-ylidene)-N-methyl-1-(4-vinylphenyl)methanaminium chloride); or poly(1-(bis(dimethylamino)methylene)-3,4-ethylenepyrrolidin-1-ium bromide).

8. The guanidinium-based polymer or copolymer of any one of claims 1 to 7, which is water-soluble.

9. A chemical mechanical planarization composition comprising the guanidinium-based polymer or copolymer of any one of claims 1 to 8.

10. An abrasive material; A guanidinium-based polymer or copolymer according to any one of claims 1 to 8; Water, optionally an activator; an oxidizing agent; A corrosion inhibitor; a dishing reducing agent; A stabilizer and and a pH adjuster.

11. 11. The chemical mechanical planarizing composition of claim 10, wherein the abrasive is selected from the group consisting of 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, and the abrasive ranges from 0.01 wt % to 30 wt %, 0.05 wt % to 20 wt %, 0.01 wt % to 10 wt %, or 0.1 wt % to 2 wt %.

12. 12. The chemical mechanical planarizing composition of claim 10 or 11, wherein the guanidinium-based polymer or copolymer is in the range of 0.00001 wt % to 1.0 wt %, 0.0001 wt % to 0.5 wt %, 0.0002 wt % to 0.1 wt %, or 0.0005 wt % to 0.05 wt %.

13. The chemical mechanical planarizing composition of any one of claims 10 to 12, wherein the abrasive is silica particles.

14. The oxidizing agent is a peroxy compound selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, propane peroxoacid, substituted or unsubstituted butane peroxoacid, hydroperoxyacetaldehyde, potassium periodate, and ammonium peroxymonosulfate, as well as ferric nitrite, KClO ４ , KBrO ４ , and KMnO ４ and combinations thereof, wherein the oxidizer is in the range of 0.01 wt % to 30 wt %, 0.1 wt % to 20 wt %, or 0.5 wt % to 10 wt %.

15. The activator is selected from the group consisting of: (1) inorganic oxide particles coated with a transition metal, the transition metal being selected from the group consisting of Fe, Cu, Mn, Co, Ce, and combinations thereof; (2) a soluble catalyst selected from the group consisting of iron (III) nitrate, ammonium iron (III) oxalate trihydrate, tribasic iron (III) citrate monohydrate, iron (III) acetylacetonate, ethylenediaminetetraacetic acid, and iron (III) sodium salt hydrate; and (3) Ag. , Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, and V, and combinations thereof, and the activator is in the range of 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 %.

16. 16. The chemical mechanical planarizing composition of claim 10, 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, triazine thiols, triazine dithiols, and triazine trithiols, pyrazoles, imidazoles, isocyanurates such as 1,3,5-tris(2-hydroxyethyl) and combinations thereof, and the corrosion inhibitor is in the range of less than 1.0 wt %, less than 0.5 wt %, or less than 0.25 wt %.

17. 17. The chemical mechanical planarizing composition of any one of claims 10 to 16, wherein the pH adjuster 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 raise the pH.

18. The chemical mechanical planarizing composition of any one of claims 10 to 17, wherein the composition has a pH of 1 to 14, 1 to 7, 1 to 6, or 1.5 to 4.

19. The dishing reducing agent may be 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 repeat units such as polyethylene oxide (PEO), ethoxylated surfactants, nitrogen-containing heterocycles not containing nitrogen-hydrogen bonds, sulfides, oxazolidines or mixtures of functional groups in one compound, nitrogen-containing compounds having 3 or more carbon atoms forming alkyl ammonium ions, aminoalkyls having 3 or more carbon atoms, at least one nitrogen-containing complex 19. The chemical mechanical planarizing composition of claim 10, wherein the dishing reducing agent is selected from the group consisting of a polymeric corrosion inhibitor containing a repeating group of heterocyclic or tertiary or quaternary nitrogen atoms, a polycationic amine compound, a cyclodextrin compound, a polyethyleneimine compound, glycolic acid, chitosan, a sugar alcohol, a polysaccharide, an alginate compound, and a sulfonic acid polymer, and combinations thereof, and the dishing reducing agent is in the range of 0.001 wt % to 2.0 wt %, 0.005 wt % to 1.5 wt %, or 0.01 wt % to 1.0 wt %.

20. 20. The chemical mechanical planarizing composition of any one of claims 10 to 19, wherein the stabilizer is selected from the group consisting of adipic acid, phthalic acid, citric acid, malonic acid, orthophthalic acid, phosphoric acid, substituted or unsubstituted phosphonic acids, nitriles, and combinations thereof, and the stabilizer is in the range of 0.0001 to 5 wt %, 0.00025 to 2 wt %, or 0.0005 to 1 wt %.

21. 21. The chemical mechanical planarizing composition of claim 10, wherein the chemical mechanical planarizing composition comprises silica particles or surface-modified silica particles; a guanidinium-based polymer or copolymer selected from the group consisting of poly(vinylbenzyl-N-(bis(dimethylamino)methylene-N-methyl)methanaminium chloride), poly(3-acrylamide-N-(bis(dimethylamino)methylene-N-methylpropan-1-aminium bromide), poly(N-(1,3-dimethylimidazolidin-2-ylidene)-N-methyl-1-(4-vinylphenyl)methanaminium chloride), poly(1-(bis(dimethylamino)methylene)-3,4-ethylenepyrrolidin-1-ium bromide), and combinations thereof; iron(III) nitrate; malonic acid; hydrogen peroxide; and water, wherein the pH of the composition is 1.5 to 4.

22. 1. A polishing method for chemical mechanical planarization of a semiconductor substrate having at least one surface containing tungsten, comprising: a) providing a polishing pad; b) providing a chemical mechanical planarizing composition, said chemical mechanical planarizing composition comprising: An abrasive material; A guanidinium-based polymer or copolymer according to any one of claims 1 to 8; Water, optionally an activator; an oxidizing agent; A corrosion inhibitor; a dishing reducing agent; A stabilizer and providing a chemical mechanical planarization composition comprising: c) polishing at least one tungsten-containing surface with the chemical mechanical planarizing composition.

23. 23. The polishing method of claim 22, wherein the abrasive is selected from the group consisting of inorganic oxide particles, metal oxide-coated inorganic oxide particles, organic polymer particles, metal oxide-coated organic polymer particles, and combinations thereof, and the abrasive is in the range of 0.01 wt % to 30 wt %, 0.05 wt % to 20 wt %, 0.01 wt % to 10 wt %, or 0.1 wt % to 2 wt %.

24. 24. The polishing method according to claim 22 or 23, wherein the guanidinium-based polymer or copolymer is in the range of 0.00001 wt % to 1.0 wt %, 0.0001 wt % to 0.5 wt %, 0.0002 wt % to 0.1 wt %, or 0.0005 wt % to 0.05 wt %.

25. The polishing method according to any one of claims 22 to 24, wherein the abrasive is silica particles or surface-modified silica particles.

26. The oxidizing agent is a peroxy compound selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, propane peroxoacid, substituted or unsubstituted butane peroxoacid, hydroperoxyacetaldehyde, potassium periodate, and ammonium peroxymonosulfate, as well as ferric nitrite, KClO ４ , KBrO ４ , and KMnO ４ and combinations thereof, wherein the oxidizing agent is in the range of 0.01 wt % to 30 wt %, 0.1 wt % to 20 wt %, or 0.5 wt % to 10 wt %.

27. The activator is selected from the group consisting of: (1) inorganic oxide particles having a surface coated with a transition metal, the transition metal being selected from the group consisting of Fe, Cu, Mn, Co, Ce, and combinations thereof; (2) a soluble catalyst selected from the group consisting of iron (III) nitrate, ammonium iron (III) oxalate trihydrate, tribasic iron (III) citrate monohydrate, iron (III) acetylacetonate, ethylenediaminetetraacetic acid, and iron (III) sodium salt hydrate; (3) The polishing method according to any one of claims 22 to 26, wherein the activator is selected from the group consisting of metal compounds having multiple oxidation states selected from the group consisting of Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, and V, and combinations thereof, and the activator is in the range of 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 %.

28. 28. The polishing method according to claim 22, 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, triazine thiol, triazine dithiol, triazine trithiol, pyrazole, imidazole, isocyanurate such as 1,3,5-tris(2-hydroxyethyl) and combinations thereof, and the corrosion inhibitor is present in an amount of less than 1.0 wt %, less than 0.5 wt %, or less than 0.25 wt %.

29. 29. The polishing method according to claim 22, wherein the pH adjuster 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 for lowering the pH; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and mixtures thereof for raising the pH.

30. The polishing method according to any one of claims 22 to 29, wherein the composition has a pH of 1 to 14, 1 to 7, 1 to 6, or 1.5 to 4.

31. The dishing reducing agent may be 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 repeat units such as polyethylene oxide (PEO), ethoxylated surfactants, nitrogen-containing heterocycles not containing nitrogen-hydrogen bonds, sulfides, oxazolidines or mixtures of functional groups in one compound, nitrogen-containing compounds having 3 or more carbon atoms that form alkyl ammonium ions, amino alkyls having 3 or more carbon atoms, and at least one nitrogen-containing heterocycle.

31. The polishing method according to claim 22, wherein the dishing reducing agent is selected from the group consisting of a polymeric corrosion inhibitor containing a repeating group of heterocycles or tertiary or quaternary nitrogen atoms, a polycationic amine compound, a cyclodextrin compound, a polyethyleneimine compound, glycolic acid, chitosan, a sugar alcohol, a polysaccharide, an alginate compound, and a sulfonic acid polymer, and combinations thereof, and the dishing reducing agent is in the range of 0.001% to 2.0% by weight, 0.005% to 1.5% by weight, or 0.01% to 1.0% by weight.

32. 32. The polishing method according to claim 22, wherein the stabilizer is selected from the group consisting of adipic acid, phthalic acid, citric acid, malonic acid, orthophthalic acid, phosphoric acid, substituted or unsubstituted phosphonic acid, nitrile, and combinations thereof, and the stabilizer is in the range of 0.0001 to 5 wt %, 0.00025 to 2 wt %, or 0.0005 to 1 wt %.

33. 33. The polishing method according to claim 22, wherein the chemical mechanical planarization composition comprises silica particles or surface-modified silica particles; a guanidinium-based polymer or copolymer selected from the group consisting of poly(vinylbenzyl-N-(bis(dimethylamino)methylene-N-methyl)methanaminium chloride), poly(3-acrylamide-N-(bis(dimethylamino)methylene-N-methylpropan-1-aminium bromide), poly(N-(1,3-dimethylimidazolidin-2-ylidene)-N-methyl-1-(4-vinylphenyl)methanaminium chloride), poly(1-(bis(dimethylamino)methylene)-3,4-ethylenepyrrolidin-1-ium bromide), and combinations thereof; iron(III) nitrate; malonic acid; hydrogen peroxide; and water, and the pH of the composition is 1.5 to 4.

34. 1. A system for chemical mechanical planarization of a semiconductor substrate having at least one surface containing tungsten, comprising: a) a polishing pad; b) a chemical mechanical planarization composition, An abrasive material; A guanidinium-based polymer or copolymer according to any one of claims 1 to 8; Water, optionally an activator; an oxidizing agent; A corrosion inhibitor; a dishing reducing agent; A stabilizer and a pH adjuster; and a chemical mechanical planarization composition comprising: The system wherein the at least one tungsten-containing surface is in contact with the polishing pad and the chemical-mechanical planarizing composition.

35. 35. The system of claim 34, wherein the chemical mechanical planarization composition has an abrasive selected from the group consisting of inorganic oxide particles, metal oxide coated inorganic oxide particles, organic polymer particles, metal oxide coated organic polymer particles, and combinations thereof in the range of 0.01% to 30%, 0.05% to 20%, 0.01% to 10%, or 0.1% to 2% by weight.

36. 36. The system of claim 34 or 35, wherein the guanidinium-based polymer or copolymer is in the range of 0.00001% to 1.0% by weight, 0.0001% to 0.5% by weight, 0.0002% to 0.1% by weight, or 0.0005% to 0.05% by weight.

37. The system of any one of claims 34 to 36, wherein the abrasive is silica particles or surface-modified silica particles.

38. The oxidizing agent is a peroxy compound selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, propane peroxoacid, substituted or unsubstituted butane peroxoacid, hydroperoxyacetaldehyde, potassium periodate, and ammonium peroxymonosulfate, as well as ferric nitrite, KClO ４ , KBrO ４ , and KMnO ４ and combinations thereof, wherein the oxidizing agent is in the range of 0.01% to 30% by weight, 0.1% to 20% by weight, or 0.5% to 10% by weight.

39. The activator is selected from the group consisting of: (1) inorganic oxide particles having a surface coated with a transition metal, the transition metal being selected from the group consisting of Fe, Cu, Mn, Co, Ce, and combinations thereof; and (2) a soluble catalyst selected from the group consisting of iron (III) nitrate, ammonium iron (III) oxalate trihydrate, tribasic iron (III) citrate monohydrate, iron (III) acetylacetonate, ethylenediaminetetraacetic acid, and iron (III) sodium salt hydrate. , (3) a metal compound having multiple oxidation states selected from the group consisting of Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, and V, and combinations thereof, and the activator is in the range of 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 %.

40. 40. The system of any one of claims 34-39, 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, triazine thiols, triazine dithiols, and triazine trithiols, pyrazoles, imidazoles, isocyanurates such as 1,3,5-tris(2-hydroxyethyl) and combinations thereof, and the corrosion inhibitor is in the range of less than 1.0 wt%, less than 0.5 wt%, or less than 0.25 wt%.

41. 41. The system of any one of claims 34-40, wherein the pH adjuster 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 for lowering the pH; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and mixtures thereof for raising the pH.

42. 42. The system of any one of claims 34 to 41, wherein the pH of the composition is 1 to 14, 1 to 7, 1 to 6, or 1.5 to 4.

43. The dishing reducing agent may be 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 repeat units such as polyethylene oxide (PEO), ethoxylated surfactants, nitrogen-containing heterocycles not containing nitrogen-hydrogen bonds, sulfides, oxazolidines or mixtures of functional groups in one compound, nitrogen-containing compounds having 3 or more carbon atoms that form alkyl ammonium ions, amino alkyls having 3 or more carbon atoms, and at least one nitrogen-containing heterocycle.

43. The system of any one of claims 34-42, wherein the dishing reducing agent is selected from the group consisting of a polymeric corrosion inhibitor containing heterocyclic or repeating groups of tertiary or quaternary nitrogen atoms, a polycationic amine compound, a cyclodextrin compound, a polyethyleneimine compound, glycolic acid, chitosan, a sugar alcohol, a polysaccharide, an alginate compound, and a sulfonic acid polymer, and combinations thereof, and the dishing reducing agent is in the range of 0.001 wt % to 2.0 wt %, 0.005 wt % to 1.5 wt %, or 0.01 wt % to 1.0 wt %.

44. 44. The system of any one of claims 34-43, wherein the stabilizer is selected from the group consisting of adipic acid, phthalic acid, citric acid, malonic acid, orthophthalic acid, phosphoric acid, substituted or unsubstituted phosphonic acids, nitriles, and combinations thereof, and the stabilizer is in the range of 0.0001 to 5 wt%, 0.00025 to 2 wt%, or 0.0005 to 1 wt%.

45. 45. The system of any one of claims 34 to 44, wherein the chemical mechanical planarization composition comprises silica particles or surface-modified silica particles; iron(III) nitrate; malonic acid; hydrogen peroxide, a guanidinium-based polymer or copolymer selected from the group consisting of poly(vinylbenzyl-N-(bis(dimethylamino)methylene-N-methyl)methanaminium chloride), poly(3-acrylamide-N-(bis(dimethylamino)methylene-N-methylpropan-1-aminium bromide), poly(N-(1,3-dimethylimidazolidin-2-ylidene)-N-methyl-1-(4-vinylphenyl)methanaminium chloride), poly(1-(bis(dimethylamino)methylene)-3,4-ethylenepyrrolidin-1-ium bromide), and combinations thereof; and water, wherein the pH of the composition is 1.5 to 4.

Images