Triazole and / or Triazolium-Based Polymers and Copolymers as Additives for Chemical Mechanical Planarization Slurries - Patent application

Abstract

The synthesis of triazole and / or triazolium-based polymers is disclosed. A chemical mechanical planarization (CMP) slurry comprises an abrasive, an activator, an oxidizer, an additive comprising a triazole and / or triazolium-based polymer, and water. The use of the synthesized triazole and / or triazolium-based polymers 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 / 251,127, filed October 1, 2021, the entire contents of which are incorporated herein by reference. [Background technology]

[0002] The present 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, the present disclosure relates to polishing slurries suitable for use in polishing patterned semiconductor wafers that include tungsten-containing metallic materials.

[0003] Integrated circuits are interconnected by the use of well-known multi-layer interconnects. The interconnect structure usually has a first layer of metallization, an interconnect layer, a second layer of metallization, and typically a third and subsequent layers of metallization. Interlayer insulating 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 by using metallized vias, particularly tungsten vias. U.S. Pat. No. 4,789,648 describes a method for preparing multiple metallized layers and metallized vias in an insulating film. Similarly, metal contacts are used to form electrical connections between the interconnect layers and devices formed within the wells. Metal vias and contacts are typically filled with tungsten, and an adhesion layer, typically titanium nitride (TiN) and / or titanium, is used to adhere the metal layer, such as the tungsten metal layer, to the insulating 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, the 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 in transistors because it has better electrical properties than polysilicon, which has traditionally been used as the 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. Although 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 the tolerance of defects 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 and chemically reactive solution, commonly referred to as a polishing "slurry", polishing "composition" or polishing "formulation", is deposited on the pad during polishing, and the rotation and / or motion of the pad relative to the wafer carries 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 driven 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 action 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. In most cases, CMP technology is advancing faster than the understanding on which it is based, as described by Seo, JA 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 requirements for device scaling and new trends in the semiconductor industry is indisputable. Numerous interactions between the wafer, slurry and pad as well as the overall process parameters determine the outcome of CMP. Finally, 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 a combination of completely different materials such as insulating materials, barriers and metal layers is 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 overpolished, resulting in a "dishing" effect. Another unacceptable defect is called "erosion," which describes the difference in topography between areas with dielectric layers 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] Specially designed water-based slurries are considered the main driving force 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. In general, 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 dishing effects in tungsten CMP processes.

[0013] U.S. Patent No. 5,876,490 describes the use of an abrasive slurry comprising abrasive particles, exhibiting a normal stress effect, and further comprising 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, the polyelectrolyte having a molecular weight of about 500 to about 10,000.

[0014] US Patent Application Publication No. 2010 / 0075501(A1) describes an aqueous dispersion for chemical mechanical polishing used to polish a polishing target including an interconnect layer containing tungsten. The aqueous dispersion for chemical mechanical polishing includes (A) a cationic water-soluble polymer, (B) an iron(III) compound, and (C) colloidal silica particles. The content of (A) the cationic water-soluble polymer (M A ) (mass%) and (B) the content of iron(III) compounds (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] US Patent Application Publication No. 2010 / 0252774(A1) describes an aqueous dispersion for chemical mechanical polishing used for polishing 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 of (A) the cationic water-soluble polymer (M A ) (mass%) and (C) the colloidal silica content (M C ) (mass%) and "M A / M C =0.0001 to 0.003". Aqueous dispersion for chemical mechanical polishing

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

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

[0018] One problem commonly encountered in CMP, especially in metal applications such as tungsten, is dishing of tungsten lines and erosion of arrays of metal lines. Dishing and erosion are important CMP parameters that define the planarity of the polished wafer. Dishing of lines typically increases for wider lines. Erosion of arrays typically increases with increasing pattern density.

[0019] 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 the overall CMP results.

[0020] Tungsten CMP slurries should be formulated to minimize dishing, erosion, and corrosion to meet specific design goals critical to device functionality.

[0021] Finding a solution to control topological 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 a desirable removal rate in polishing. Summary of the Invention

[0022] The present invention fills this need by providing a tungsten CMP slurry, a system and method for using the CMP slurry that is intelligently designed to minimize the noted problems of dishing and erosion in highly selective tungsten slurries while maintaining desirable polishing of metal layers, particularly tungsten films.

[0023] Polymer additives play an important role as dispersants and passivators in slurry development to obtain the desired removal rate, selectivity and degree of defectivity.

[0024] The present invention discloses the synthesis of triazole and triazolium based polymers or copolymers and demonstrates the use of the synthesized triazole and triazolium based polymers or copolymers in CMP slurries to reduce the described problems by tailoring removal rate and selectivity, as well as reducing dishing and erosion to control overall topography.

[0025] Triazole and / or triazolium based polymers or copolymers are cationic polymers or copolymers formed by at least one monomer having at least one triazole or triazolium group or having at least one repeat unit having at least one triazole or triazolium group.

[0026] In addition, some specific aspects of the present invention are outlined below. Embodiment 1: A triazole- or triazolium-based polymer or copolymer, comprising: (1) has at least one triazole or triazolium group; and [ka] [In the formula, P1 is a polymerizable group; Sp1 is a spacer group or a single bond; R1, R2 are each independently selected from the group consisting of H, substituted or unsubstituted aliphatic, aromatic, heteroaromatic or siloxane moieties, CH2 not in an aromatic or heteroaromatic ring may be replaced with O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced with F, Cl or CN; R3 is a substituted or unsubstituted linear, cyclic or branched aliphatic group; or R3 has the formula Q, [ka] [In the formula, Sp2 is a spacer group or a single bond, which may be the same as or different from Sp1; selected from the group consisting of substituted or unsubstituted linear, cyclic or branched aliphatic groups, CH2 may be replaced with O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced with F, Cl or CN; P2 is a polymerizable group which may be the same as or different from P1; it is a group containing a C=C double bond. X - is an anionic counterion] or is formed by at least one monomer comprising a structure selected from the group consisting of (2) [ka] [In the formula, L is a spacer group or a single bond; R1, R2 and R3 are each independently selected from the group consisting of H or a substituted or unsubstituted aliphatic, aromatic, heteroaromatic or siloxane moiety, where CH2 not in an aromatic or heteroaromatic ring may be replaced with O, S or N such that the heteroatoms are not bonded to each other, and hydrogen may be replaced with F, Cl or CN; n is an integer from 1 to 6000; X - is an anionic counterion] A triazole- or triazolium-based polymer or copolymer having at least one repeat unit having a structure selected from the group consisting of: Aspect 2: A triazole or triazolium based polymer or copolymer according to aspect 1, wherein the polymerizable group P1 is selected from the group consisting of vinyl, styrene, acrylic or methacrylic, acrylamide, methacrylamide, ethylene glycol, vinyl ether, siloxane, phenol, norbornene type backbone, and combinations thereof, preferably a group containing a C=C double bond. Embodiment 3: A triazole- or triazolium-based polymer or copolymer according to embodiment 1 or 2, wherein the spacer group or the single bond Sp1 or L is selected from the group consisting of substituted or unsubstituted linear, cyclic or branched aliphatic groups, CH2 may be optionally replaced by O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be optionally replaced by F, Cl or CN. Aspect 4: Anionic counterion X - is a halide (F - , Cl - , Br - , or I - ), BF4 - , PF6 - , carboxylate, malonate, citrate, carbonate, fumarate, MeOSO3 - , MeSO3 - , CF3COO - , CF3SO3 - 4. The triazole or triazolium based polymer or copolymer according to any one of claims 1 to 3, wherein the triazole or triazolium based polymer or copolymer is selected from the group consisting of: nitrates, and sulfates. Embodiment 5: A triazole or triazolium based polymer or copolymer according to embodiments 1 to 4, wherein the spacer group or the single bond Sp1 or L is selected from the group consisting of substituted or unsubstituted linear, cyclic or branched aliphatic groups, CH2 may be optionally replaced by O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be optionally replaced by F, Cl or CN. Aspect 6: The triazole or triazolium based polymer or copolymer according to aspects 1-5, wherein the polymerization is 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 7: A triazole- or triazolium-based polymer or copolymer according to embodiments 1-6, wherein the copolymer has block copolymer properties. Aspect 8: The triazole or triazolium based polymer or copolymer is the triazole or triazolium based polymer or copolymer according to aspects 1-7, including, but not limited to, poly(vinyl-4-ethyl-1,2,4-triazol-4-ium) bromide; poly(vinyl-4-ethyl-1,2,4-triazol-4-ium-co-vinylpyrrolidone) bromide; poly(vinyl-1,2,4-triazole-co-vinylpyrrolidone); and poly(vinyl-4-ethyl-1,2,4-triazol-4-ium-co-vinyl-1,2,4-triazole) bromide. Aspect 9: Abrasives and An activator; An oxidizing agent; An additive comprising a triazole- or triazolium-based polymer or copolymer according to any one of aspects 1 to 8; Water, optionally A corrosion inhibitor; A dishing reducing agent; A stabilizer, A pH adjuster, 1. A chemical mechanical planarization composition comprising: Aspect 10: 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 according to embodiment 9; Equipped with 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. Embodiment 11: 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 9; c) polishing at least one tungsten-containing surface with a chemical mechanical planarization composition; A polishing method comprising:

[0027] 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.

[0028] 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.

[0029] 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.

[0030] Organic polymer particles include, but are not limited to, polystyrene particles, polyurethane particles, polyacrylate particles, or any other organic polymer particles.

[0031] Metal oxide coated organic polymer particles include, but are not limited to, ceria coated organic polymer particles, zirconia coated organic polymer particles.

[0032] 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. n Group, M can be, for example, sodium, potassium, or ammonium. An example of such a surface chemistry modified silica particle includes, but is not limited to, Fuso PL-2C manufactured by Fuso Chemical Company.

[0033] 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.

[0034] Activators include, but are not limited to, (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) soluble catalysts selected from the group consisting of iron (III) nitrate, ammonium iron (III) oxalate trihydrate, iron (III) citrate tribasic 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.

[0035] The activator is in the range of 0.00001% to 5.0% by weight, 0.0001% to 2.0% by weight, 0.0005% to 1.0% by weight, or 0.001% to 0.5% by weight.

[0036] 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 peroxoacid, substituted or unsubstituted butane peroxoacid, hydroperoxyacetaldehyde, potassium periodate, ammonium peroxymonosulfate, and non-peroxy compounds selected from the group consisting of ferric nitrite, KClO4, KBrO4, KMnO4.

[0037] The oxidizing agent concentration can range from about 0.01% to 30% by weight, with a preferred concentration of the oxidizing agent being from about 0.1% to 20% by weight and a more preferred concentration of the oxidizing agent being from about 0.5% to about 10% by weight. The weight percentages are of the composition.

[0038] The overall amount of additives including triazole and / or triazolium based polymers or copolymers ranges from 0.00001% to 1%, 0.0001% to 0.5%, 0.0002% to 0.1%, or 0.0005% to 0.05% by weight.

[0039] 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.

[0040] Suitable pH adjusters for increasing the pH of the polishing composition include, but are not limited to, potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and mixtures thereof.

[0041] The pH of the slurry is 1-14, preferably 1-7, more preferably 1-6, and most preferably 1.5-4.

[0042] The CMP slurry may further include surfactants, dispersants, chelating agents, film-forming corrosion inhibitors, and biocides.

[0043] Other aspects, features and embodiments of the present invention will become more fully apparent from the following disclosure and appended claims.

[0044] The embodiments of the present invention may be used alone or in combination with each other. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0045] 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.

[0046] More specifically, the present invention discloses the synthesis of triazole and triazolium based polymers or copolymers and demonstrates the use of the synthesized triazole and triazolium based polymers or copolymers in CMP slurries to reduce the noted problems by tailoring removal rate and selectivity, as well as reducing dishing and erosion to control overall topography.

[0047] 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.

[0048] 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 the overall CMP results.

[0049] Certain water-soluble cationic polymers are key elements in the 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 the slurry development to obtain the desired removal rate, selectivity and degree of defectivity.

[0050] Triazole-based molecules have a variety of applications. They have diverse property profiles in medicine, agriculture or material science. Low molecular weight triazoles are well-known corrosion inhibitors for various metals and components of many modern slurries. The abundance of π electrons and unshared electron pairs on the nitrogen atom of the five-membered ring can interact with the d-orbitals of metals and provide a protective film to inhibit corrosion, as described in Phadke Swathi, N.; Alva, VDP; Samshuddin, SA Review on 1,2,4-Triazole Derivatives as Corrosion Inhibitors. Journal of Bio-and Tribo-Corrosion 2017, 3(4), 42.

[0051] Among the polymers used in CMP slurries, triazole- or triazolium-based polymers have surprisingly not been described as additives for CMP slurries.

[0052] Polymers with triazole or triazolium structures are not only characterized by their interaction with metal atoms, but also, due to their cationic nature, they can electrostatically interact with some oppositely charged surfaces, leading to positive effects on removal rate, selectivity and CMP defects.

[0053] Triazole and / or triazolium based polymers or copolymers are cationic polymers or copolymers formed by at least one monomer having at least one triazole or triazolium group or having at least one repeat unit having at least one triazole or triazolium group. Triazole or triazolium based polymers or copolymers include homopolymers, random copolymers and block copolymers.

[0054] Surprisingly, it has been found that the described triazole or triazolium-based polymer or copolymer can electrostatically interact with negatively charged metal layers, such as tungsten surfaces, and inhibit the removal of metal during CMP.Specific designed polymers can be used to prevent overpolishing effects and reduce erosion and dishing.As a result, triazolium-based polymers or copolymers are promising candidates for overall topography control, especially for reducing dishing and erosion.

[0055] All references cited in this specification, including publications, patent applications, and patents, are hereby 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.

[0056] In the context of describing the present invention (particularly in the context of the claims below), the use of the terms "a" and "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 individual value falling within the range, unless otherwise indicated herein, and each individual 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 limitations 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. Use of the term "comprising" in this specification and claims includes the narrower terms "consisting essentially of" and "consisting of."

[0057] 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 of ordinary skill in the art upon reading the foregoing description. The inventors anticipate that those of ordinary skill in the art will employ such variations as appropriate, and the inventors intend for the invention to 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. Moreover, 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.

[0058] For ease of reference, "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 circuit, 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 meant to be limiting in any way and includes any substrate that will ultimately become a microelectronic device or microelectronic assembly.

[0059] "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.

[0060] As used herein, "about" is intended to correspond to ±5%, preferably ±2% of the stated value.

[0061] 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.

[0062] There are several specific aspects of the present invention.

[0063] One embodiment is for the synthesis of triazole- or triazolium-based polymers or copolymers 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.

[0064] 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 triazole and / or triazolium-based cationic polymer or copolymer, and water; 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.

[0065] The CMP slurry may further include surfactants, dispersants, chelating agents, film-forming corrosion inhibitors, biocides, and polishing enhancers.

[0066] 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; Equipped with 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.

[0067] Yet another aspect is a polishing method for chemical mechanical planarization of a semiconductor substrate having at least one surface containing tungsten, comprising: contacting the at least one surface containing tungsten with a polishing pad; delivering a chemical mechanical planarization composition; polishing the at least one surface containing tungsten with a chemical mechanical planarization composition; The polishing method includes the steps of:

[0068] Abrasives 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.

[0069] The abrasives used in the CMP slurry may be activator-containing particles (ie, abrasives having an activator coating) or non-activator-containing particles.

[0070] Inorganic oxide particles include, but are not limited to, ceria, silica, alumina, titania, germania, spinel, oxides or nitrides of tungsten, zirconia particles, or any of the above doped with one or more other minerals or elements, and any combination thereof.Oxide abrasives can be made by any of a variety of techniques, including sol-gel, hydrothermal, hydrolysis, plasma, pyrolysis, aerogel, fuming and precipitation methods, and any combination thereof.

[0071] Precipitated inorganic oxide particles can be obtained by known methods by reaction of metal salts and acids or other precipitants. Pyrolytic metal oxide and / or metalloid oxide particles can be obtained by hydrolysis of suitable vaporizable starting materials in an oxygen / hydrogen flame. An example is pyrogenic 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 their chemical and physical mixtures, are suitable.

[0072] 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.

[0073] The metal oxide coated organic polymer particles are selected from the group consisting of ceria coated organic polymer particles, zirconia coated organic polymer particles.

[0074] Organic polymer particles include, but are not limited to, polystyrene particles, polyurethane particles, polyacrylate particles, or any other organic polymer particles.

[0075] 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.

[0076] 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 such silica particle surfaces to have different chemical functional groups and to have positive or negative charges at 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.

[0077] An example of such a surface chemistry modified silica particle includes, but is not limited to, Fuso PL-2C manufactured by Fuso Chemical Company.

[0078] 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.

[0079] 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 10-700 nm, about 20-500 nm, or about 30-300 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.

[0080] The abrasive particles may be purified using a suitable method, such as ion exchange, to remove metal impurities that may help improve colloidal stability. Alternatively, high purity abrasive particles are used.

[0081] 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.

[0082] 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.

[0083] Additives The CMP slurry of the present invention includes an additive which is a triazole and / or triazolium based polymer or copolymer.

[0084] The triazole or triazolium 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.

[0085] A triazole- or triazolium-based polymer or copolymer is a cationic polymer or copolymer formed by at least one monomer having at least one triazole or triazolium group, the monomer being [ka] [In the formula, P1 represents a polymerizable group; Sp1, in each occurrence, represents a spacer group or a single bond; R1, R2 are each independently H or a substituted or unsubstituted aliphatic, aromatic, heteroaromatic or siloxane moiety, where CH2 not in an aromatic or heteroaromatic ring may be replaced with O, S or N such that the heteroatoms are not bonded to each other, and hydrogen may be replaced with F, Cl or CN; R3 is a substituted or unsubstituted linear, cyclic or branched aliphatic group; or R3 has the formula Q, [ka] [In the formula, Sp2 is a spacer group or a single bond, which may be the same as or different from Sp1; selected from the group consisting of substituted or unsubstituted linear, cyclic or branched aliphatic groups, CH2 may be replaced with O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced with F, Cl or CN; P2 is a polymerizable group which may be the same as or different from P1; it is a group containing a C=C double bond. X - represents an anionic counterion] The structure includes a structure selected from the group consisting of:

[0086] Polymerizable groups P1 include, but are not limited to, groups containing a C=C double bond.

[0087] At each occurrence, the spacer group or single bond Sp1 may include, but is not limited to, substituted or unsubstituted, linear, cyclic or branched aliphatic groups, CH2 may be replaced with O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced with F, Cl or CN.

[0088] 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, and Me is methyl.

[0089] The triazole and / or triazolium based polymer or copolymer may be [ka] [In the formula, L, at each occurrence, represents a spacer group or a single bond; R1, R2 and R3 are each independently H or a substituted or unsubstituted aliphatic, aromatic, heteroaromatic or siloxane moiety, where CH2 not in an aromatic or heteroaromatic ring may be replaced with O, S or N such that the heteroatoms are not bonded to each other, and hydrogen may be replaced with F, Cl or CN; n is an integer from 1 to 6000; X - represents an anionic counterion] A cationic polymer or copolymer having repeating units having a structure selected from the group consisting of:

[0090] Spacer groups L include, but are not limited to, substituted or unsubstituted, linear, cyclic or branched aliphatic groups, in which CH2 may be replaced with O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced with F, Cl or CN.

[0091] Anionic counterion X - As for the halides (F - , Cl - , Br - , I - ), BF4 - , PF6 - , carboxylate, malonate, citrate, carbonate, fumarate, MeOSO3 - , MeSO3 - , CF3COO - , CF3SO3 - , nitrates or sulfates, but are not limited to these.

[0092] The overall amount of additives including triazole and / or triazolium based polymers or copolymers ranges from 0.00001% to 1%, 0.0001% to 0.5%, 0.0002% to 0.1%, or 0.0005% to 0.05% by weight.

[0093] Oxidizing agent The CMP slurry of the present invention includes an oxidizing agent or oxidizer for chemical etching of materials.

[0094] 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 material 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 aid in the chemical removal process, but as low as possible to minimize similar or related issues, such as handling, environmental issues, or cost.

[0095] Advantageously, in one embodiment of the present invention, the oxidizing agent is a component that generates free radicals when exposed to at least one activating agent, which increases the etch rate at least on selected structures. The free radicals described below oxidize most metals, making the surface more susceptible to oxidation from other oxidizing agents. However, the oxidizing agents are listed separately from the "compounds that generate free radicals" discussed below, because some oxidizing agents do not readily form free radicals when exposed to an activating agent, and in some embodiments, it is advantageous to have one or more oxidizing agents that provide a matched or preferential etch rate for various combinations of metals that may be found on a substrate.

[0096] As is known in the art, some oxidizers are more suitable for certain components than others. In some embodiments of the invention, the selectivity of the CMP system for one metal as opposed to another metal is maximized, as is known in the art. However, in certain embodiments of the 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.

[0097] In one embodiment, the oxidizing agent is an inorganic or organic percompound.

[0098] Percompounds are generally defined as compounds that contain an element in its highest oxidation state, such as perchloric acid, or compounds that contain at least one peroxy group (-OO-), such as peracetic acid and perchromate.

[0099] 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.

[0100] Suitable per compounds containing at least one peroxy group include peroxides. As used herein, the term "peroxide" includes 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 the above 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 includes common examples such as hydrogen peroxide, peroxyformic acid, peracetic acid, propane peroxoacid, substituted or unsubstituted butane peroxoacid, hydroperoxy-acetaldehyde, and the like, and also includes common complexes of peroxides, such as urea peroxide.

[0101] Suitable percompounds containing at least one peroxy group include persulfates.As used herein, the term "persulfates" includes monopersulfates, dipersulfates, and their acids and salts and adducts.For example, peroxydisulfates, peroxymonosulfates and / or peroxymonosulfates, Caro's acid, for example, includes salts such as potassium peroxymonosulfate, but preferably non-metal salts such as ammonium peroxymonosulfate.

[0102] Suitable per-compounds containing at least one peroxy group include perphosphates, including peroxydiphosphates, as defined above.

[0103] Ozone is also a suitable oxidizing agent, either alone or in combination with one or more other suitable oxidizing agents.

[0104] 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").

[0105] Other oxidizing agents are also suitable components of the compositions of the present invention. Iodate is a useful oxidizing agent.

[0106] Two or more oxidizers may be combined to provide synergistic performance benefits.

[0107] In most embodiments of the 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, ammonium peroxymonosulfate, and non-peroxy compounds selected from the group consisting of ferric nitrite, KClO4, KBrO4, KMnO4.

[0108] In some embodiments, the preferred oxidizing agent is hydrogen peroxide.

[0109] The oxidizing agent concentration can range from about 0.01% to 30% by weight, with a preferred concentration of the oxidizing agent being from about 0.1% to 20% by weight and a more preferred concentration of the oxidizing agent being from about 0.5% to about 10% by weight. The weight percentages are of the composition.

[0110] 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.

[0111] 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.

[0112] The activator may be a non-metal-containing compound. Iodine is useful, for example, to form free radicals with hydrogen peroxide.

[0113] If the activator is a metal ion or metal-containing compound, the activator is present in a thin layer bound 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.

[0114] Activators include, but are not limited to, (1) inorganic oxide particles having a surface coated with a transition metal, the transition metal being 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.

[0115] 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.

[0116] water The polishing composition is water-based and therefore includes 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 residue, and as a diluent.Preferably, the water used in the cleaning composition is deionized (DI) water.

[0117] For most applications, the water will comprise, for example, about 10 to about 90% or 90% water by weight. Other preferred embodiments may comprise about 30 to about 95% water by weight. Still other preferred embodiments may comprise about 50 to about 90% water by weight. Still other preferred embodiments may comprise water in an amount to achieve the desired weight percentages of the other ingredients.

[0118] 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, triazinethiols, triazinedithiols, and triazinetrithiols, pyrazoles, imidazoles, isocyanurates such as 1,3,5-tris(2-hydroxyethyl) and mixtures thereof. Preferred corrosion inhibitors are 1,2,4-triazole, 5-aminotriazole, and 1,3,5-tris(2-hydroxyethyl) isocyanurate.

[0119] 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%.

[0120] Dishing reduction agent (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 having 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 having 3 or more carbon atoms forming alkylammonium ions, aminoalkyls having 3 or more carbon atoms, polymeric corrosion inhibitors containing at least one nitrogen-containing heterocycle or repeat group of tertiary or quaternary nitrogen atoms, polycationic amine compounds, cyclodextrin compounds, polyethyleneimine compounds, glycolic acid, chitosan, sugar alcohols, polysaccharides, alginate compounds, sulfonic acid polymers. Glycine is a preferred dishing reducing agent.

[0121] 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.

[0122] Stabilizer (optional) The composition may also include one or more of various optional additives. Suitable optional additives include stabilizers. These optional additives are generally used to facilitate or promote the 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, including compounds that generate free radicals, by isolating activator materials, by quenching free radicals, or by otherwise stabilizing compounds that form free radicals.

[0123] 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 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 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 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, having multiple oxidation states. In some preferred embodiments of the invention, the fluid composition contacting the substrate has less than 50 ppm, preferably less than 20 ppm, more preferably less than 10 ppm of dissolved total metals, excluding tin and zinc.

[0124] Since metals in solution are generally not recommended, non-metal-containing oxidizers that are typically present in a salt form, such as a persulfate, are preferably in the acid form and / or the ammonium salt form, such as ammonium persulfate.

[0125] Other stabilizers include free radical quenchers. As mentioned above, these attenuate the effect of the generated free radicals. Therefore, they are preferably present in small amounts, if present at all. Most antioxidants, i.e., vitamin B, vitamin C, citric acid, etc., are free radical quenchers. Most organic acids are free radical quenchers, but three that are effective and have other beneficial stabilizing properties are phosphonic acid, the binding agent oxalic acid, and the non-radical scavenging sequestering agent gallic acid.

[0126] In addition, carbonates and phosphates are believed to bind to the activator and prevent fluid access. Carbonates are particularly useful as they can be used to stabilize the slurry, but small amounts of acid can quickly remove the stabilizing ions. A useful stabilizer for absorbed activators may be a film former that forms a film on the silica particles.

[0127] 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 the activator material and thereby reduce the reaction that degrades the oxidizer, as well as any combination of the aforementioned agents. As used herein, acid stabilizing agent refers to both the acid stabilizer and its conjugate base. That is, various acid stabilizers may also be used in their conjugated form. By way of example, for the acid stabilizers mentioned above in this specification, an adipic acid stabilizer includes adipic acid and / or its conjugate base, and a carboxylic acid stabilizer includes a carboxylic acid and / or its conjugate base, carboxylate, and the like. 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 mixed into a CMP slurry.

[0128] 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 with the least adverse effect on the effectiveness of the CMP system. In general, any of these optional additives should be present in an amount sufficient to substantially stabilize the composition. The amount required will vary depending on the particular additive selected and the particular configuration of the CMP composition, such as the surface properties of the polishing 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.

[0129] Generally, suitable amounts of these stabilizers range from about 0.0001 to 5% by weight of the composition, preferably from about 0.00025 to 2% by weight, and more preferably from about 0.0005 to about 1% by weight. The stabilizers may be added directly to the composition or may be applied to the surface of the abrasive component of the composition.

[0130] pH adjuster (optional) The composition disclosed herein comprises a pH adjuster.The pH adjuster is typically used in the composition disclosed herein to increase or decrease the pH of the polishing composition.The pH adjuster can be used as necessary to improve the stability of the polishing composition, adjust the ionic strength of the polishing composition, and improve the safety in handling and use.

[0131] 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.

[0132] When used, the amount of the pH adjuster is preferably in the range of about 0.01% to about 5.0% by weight, based on the total weight of the polishing composition, with a preferred range being about 0.01% to about 1% by weight or about 0.05% to about 0.15% by weight.

[0133] The pH of the slurry is 1-14, preferably 1-7, more preferably 1-6, and most preferably 1.5-4.

[0134] Surfactant (optional) The compositions disclosed herein optionally include a surfactant, which in part protects the wafer surface during and after polishing to help reduce defects on the wafer surface.Surfactants can also be used to control the removal rate of some of the films used in polishing, such as low-K insulating films.Suitable surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof.

[0135] Non-ionic 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 dodecyl dimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amine, fluorosurfactants.

[0136] The molecular weight of the surfactants can range from a few hundred to over a million. The viscosity of these materials also has a very wide distribution.

[0137] 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 this type of surfactant include, but are not limited to, potassium ions, ammonium ions, and other cations. The molecular weight of these anionic surface wetting agents ranges from several hundred to several hundred thousand.

[0138] Cationic surfactants have a net positive charge on the main portion of the molecular backbone. Cationic surfactants are typically molecular halides that contain a hydrophobic chain and a cationic charge center, such as amines, quaternary ammonium, benzalkonium, and alkylpyridinium ions.

[0139] 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 amine or ammonium, such as the phospholipids phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelin.

[0140] 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, and 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.

[0141] If used, the amount of surfactant typically ranges from about 0.0001% to about 1.0% by weight, based on the total weight of the barrier CMP composition, and if used, the preferred range is from about 0.010% to about 0.1% by weight.

[0142] Chelating Agent (Optional) Chelating agents may be optionally 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 staining and removal rate instability. 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-diamino-benzosulfonic 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, such as glycine, serine, proline, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan, valine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, ornithine, selenium, arginine ... tein, tyrosine, sarcosine, vicine, tricine, aceglutamide, n-acetylaspartic acid, acetylcarnitine, acetylcysteine, n-acetylglutamic acid, acetylleucine, acivicine, s-adenosyl-l-homocysteine, agaritine, alanosine, aminohippuric acid, l-arginine ethyl ester, aspartame, aspartylglucosamine, benzylmercaptouric acid, biocytin, brivanib alaninate, carbocysteine, n(6)-carboxymethyllysine, calcivirin, glutamic acid, cilastatin, sitiolone, coprin, 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, no Examples of the anti-inflammatory agents include, but are not limited to, parin, octopine, ombrabulin, opine, orsanilic acid, oxaceprol, polylysine, remacemide, salicylic acid, silk amino acid, stampeidin, tabtoxin, tetrazolylglycine, thiorphan, thymectacin, tiopronin, tryptophan tryptophylquinone, valacyclovir, valganciclovir, phosphonic acid and its derivatives, such as octylphosphonic acid, aminobenzylphosphonic acid, and combinations thereof and salts thereof.

[0143] For example, chelating agents may be used where necessary to chemically bind copper and tantalum cations to facilitate dissolution of the copper and tantalum oxides to obtain the desired removal rate of copper lines, vias or trenches and barrier layers or films.

[0144] 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.

[0145] Biocide (optional) The CMP formulations disclosed herein may also include 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.

[0146] Preferred biocides are the isothiozilone compounds, such as methylisothiazolinone, methylchloroisothiazolinone, and benzoisothiazolinone.

[0147] 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.

[0148] The compositions disclosed herein may be produced 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 produced with two or more components that can be mixed before use. EXAMPLES

[0149] General Experimental Procedures All percentages are by weight unless otherwise indicated.

[0150] Part I. Synthesis Triazole and / or Triazolium 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.

[0151] Characterization methods

[0152] 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 against the internal standard Si(OMe)4 (0.00 ppm).

[0153] The polymers were analyzed by size exclusion chromatography (SEC) performed at 40 °C in H2O / MeOH / EtOAc (54 / 23 / 23, v / v / v) containing 10 mM sodium acetate (flow rate: 0.5 mL / min). Measurements were performed on an Agilent 1260 HPLC equipped with a column set consisting of a PSS Novema precolumn and a PSS Novema MAX ultraheigh column. Samples were dissolved at 50 °C in the eluent containing 0.1% ethylene glycol as an internal standard. The average molar mass of the polymers was derived from the refractive index signal based on a poly(2-vinylpyridine) calibration curve.

[0154] Example 1 Synthesis of poly(vinyl-4-ethyl-1,2,4-triazol-4-ium) bromide [ka]

[0155] Monomer synthesis [ka]

[0156] 1-Vinyl-1,2,4-triazole (CAS: 2764-83-3, 10 g, 105 mmol) was dissolved in bromoethane (CAS: 74-96-4, 57.3 g, 526 mmol). The reaction mixture was then stirred at reflux for 5 days, cooled to room temperature, and added to ethyl acetate (0.7 L), which precipitated a white solid. The solid was washed three times with ethyl acetate and dried in vacuum (13 g, 60.6% yield).

[0157] 1 H NMR(500MHz,DMSO-d6)δ:10.48(s,1H),9.40(s,1H),7.53(dd,J=15.3,8.6Hz,1H),6.08(dd,J= 15.3,1.8Hz,1H),5.58(dd,J=8.6,1.9Hz,1H),4.32(q,J=7.3Hz,2H),1.50(t,J=7.3Hz,3H)ppm.

[0158] The polymer was synthesized by a free radical polymerization process as shown below. [ka]

[0159] 4-Ethyl-1-vinyl-1H-1,2,4-triazol-4-ium bromide (5 g, 24.5 mmol) and AIBN (16.4 mg, 0.1 mmol) were dissolved in 30 mL of DMF / HO (1:1, v / v). The solution was purged with Ar for 30 min, heated at 65° C. for 24 h, cooled to room temperature, and precipitated by adding ethyl acetate to give a white solid after drying in vacuum (4.5 g, 90% yield).

[0160] 1 H NMR (500 MHz, DMSO-d6) δ: 10.64 (broad signal), 9.54-8.96 (m), 4.70 (broad signal), 4.70 (broad signal), 2.95-2.00 (m), 1.78-1.06 (m) ppm.

[0161] SEC: Mn: 26.7kDa, Mw: 128.2kDa, PDI: 4.8.

[0162] Example 2 Synthesis of poly(vinyl-4-ethyl-1,2,4-triazol-4-ium-co-vinylpyrrolidone) bromide [ka]

[0163] The polymer was synthesized by a free radical polymerization process as shown below. [ka]

[0164] 4-Ethyl-1-vinyl-1H-1,2,4-triazol-4-ium bromide (5.2 g, 25.8 mmol), 1-vinyl-2-pyrrolidone (CAS: 88-12-0, 0.96 g, 8.6 mmol) and AIBN (CAS: 78-67-1, 20.5 mg, 0.12 mmol) were dissolved in 40 mL of DMF / HO (1:1, v / v). The solution was purged with Ar for 30 min, heated at 65 °C for 24 h, cooled to room temperature and precipitated by adding ethyl acetate to give a white solid after drying in vacuum (4.9 g, 80% yield).

[0165] 1 H NMR (500 MHz, DMSO-d6) δ: 10.53 (broad signal), 9.63-8.89 (m), 4.62 (broad signal), 4.26 (broad signal), 2.32 (broad signal), 2.04 (broad signal), 1.52 (broad signal) ppm.

[0166] SEC: Mn: 41.7kDa, Mw: 353kDa, PDI: 8.5.

[0167] Example 3 Synthesis of poly(vinyl-1,2,4-triazole-co-vinylpyrrolidone) [ka]

[0168] The polymer was synthesized by a free radical polymerization process as shown below. [ka]

[0169] 1-Vinyl-1,2,4-triazole (CAS: 2764-83-2; 7.7 g, 81 mmol), 1-vinyl-2-pyrrolidone (CAS: 88-12-0, 3 g, 27 mmol) and AIBN (CAS: 78-67-1, 35.1 mg, 0.214 mmol) were dissolved in 60 mL of DMF / HO (1:1, v / v). The solution was purged with Ar for 30 min, heated at 65 °C for 24 h, cooled to room temperature and precipitated by adding ethyl acetate to give a white solid after drying in vacuum (4.4 g, 41% yield).

[0170] 1 H NMR (500 MHz, DMSO-d6) δ: 8.46-7.49 (broad m), 4.04 (broad s), 3.82-2.55 (broad m), 2.35-1.38 (broad m). ppm.

[0171] SEC: Mn: 24.1kDa, Mw: 431.3kDa, PDI: 17.9.

[0172] Example 4 Synthesis of poly(vinyl-4-ethyl-1,2,4-triazol-4-ium-co-vinyl-1,2,4-triazole) bromide [ka]

[0173] The polymer was synthesized by a free radical polymerization process as shown below. [ka]

[0174] 4-Ethyl-1-vinyl-1H-1,2,4-triazol-4-ium bromide (2.3 g, 11.0 mmol), 1-vinyl-1,2,4-triazole (CAS: 2764-83-2; 0.35 g, 3.7 mmol) and 2,2'-azobis-(2-methyl-propionamidine)-dihydrochloride (V50, CAS: 2997-92-4, 7 mg, 0.026 mmol) were dissolved in 10 mL of HO. The solution was purged with Ar for 30 min, heated at 100 °C for 24 h, cooled to room temperature and precipitated by adding THF to give a white solid after drying in vacuum (2.5 g, 96% yield).

[0175] 1 H NMR (500 MHz, DMSO-d6) δ: 10.75 (broad s), 10.31 (broad s), 9.29-9.11 (broad m), 8.39 (broad s), 7.79-7.63 (broad m), 4.64 (broad s), 4.27 (broad s), 2.36 (broad s), 1.53 (broad s) ppm.

[0176] SEC: Mn: 136.5kDa, Mw: 1182kDa, PDI: 8.7.

[0177] 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.

[0178] The polishing composition employs the synthetic triazole and / or triazolium-based polymers or copolymers of Part I.

[0179] In the examples presented below, CMP experiments were performed using the procedures and experimental conditions set out below. Parameters: Å: Angstrom - unit of length BP: Back pressure, in psi CMP: chemical mechanical planarization = chemical mechanical polishing CS: Carrier Speed DF: Downforce: pressure applied during CMP, unit: psi min:minutes mL: milliliter mV: millivolt psi: pounds per square inch PS: Platen rotation speed of the polishing tool, unit: rpm (revolutions per minute) SF: flow rate of polishing composition, mL / min TEOS: Chemical vapor deposition using tetraethyl orthosilicate as a precursor. Silicon oxide film by (CVD) Wt%: Weight percentage (of the 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.

[0180] 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.

[0181] Silicon wafers with a diameter of 200 mm coated with tungsten, TEOS, SiN or tungsten-containing SKW patterned structures were obtained from SKW Associates, Inc. 2920 Scott Blvd, Santa Clara, CA 95054. The polishing time for blanket films was 1 minute. Sheet resistance measurement techniques were used to measure tungsten removal rates. Optical techniques were used to measure TEOS removal. Patterned wafers were polished on an Ebara polisher for a set time based on eddy current techniques. The polishing time for patterned wafers was 15 seconds past the endpoint identified by eddy current endpoint techniques. Patterned wafers were analyzed with a KLA Tencor P15 Profiler (large feature size) or AFM tool (small feature size).

[0182] 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 down force of 2.5 psi.

[0183] 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, while rotating the platen and substrate. A polishing composition (slurry) was applied (usually continuously) onto the pad during the CMP process for effective removal of material and planarization of the substrate.

[0184] 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.

[0185] In the following examples, a base CMP slurry was made with 0.01 wt% ferric nitrate (iron(III) nitrate), 0.08 wt% malonic acid (stabilizer), 2.0 wt% hydrogen peroxide, 0.1 wt% glycine, and 0.25 wt% Fuso PL-2C silica particles in water. All examples had a pH adjusted to 2.3 with nitric acid.

[0186] The effect of triazole or triazolium based polymers on tungsten removal rate, erosion and dishing was examined.

[0187] Example 1 A working CMP slurry was made by adding the triazole or triazolium based polymers and copolymers described in Part I to a base CMP slurry.

[0188] The tungsten removal rate results are shown in Table 1.

[0189] Various amounts of triazole or triazolium based polymers and copolymers (10, 50, 100 ppm) were used to determine their effect on erosion and dishing.

[0190] As shown in Table 1, working CMP slurries with small amounts of the synthesized triazole or triazolium-based polymers and copolymers (approximately 10-100 ppm) provided high tungsten removal rates. Within the concentration range tested, increasing concentrations had diminishing effects on tungsten removal. [Table 1]

[0191] Example 2 A working CMP slurry was made by adding the triazole or triazolium based polymers and copolymers described in Part I to a base CMP slurry.

[0192] Table 2 summarizes the tungsten, TEOS, and SiN removal rates for working CMP slurries containing the synthesized triazole or triazolium based polymers and copolymers.

[0193] As shown in Table 2, the working CMP slurry provided high W removal rates and low TEOS and SiN removal rates, and therefore high W:TEOS RR and W:SiN RR selectivities. [Table 2]

[0194] Different patterned structures with different line features (dishing: 50 / 50 μm, erosion: 7 / 3 μm) at 20% overpolish for various formulations are summarized in Table 3. [Table 3]

[0195] As shown in Table 3, the working CMP slurry provided less than 1000 Å for 50×50 μm W interconnect dishing and less than 500 Å erosion for 7×3 μm patterned structures, which meets the needs of W polishing.

[0196] Thus, working CMP slurries using the synthesized triazole or triazolium based polymers and copolymers provide high selectivity (as shown in Table 2) while providing erosion levels of less than 500 Å.

[0197] Example 3 The effect of two different concentrations of triazolium-based polymer additives on different film polishing removal rates and W:TEOS, W:SiN or W:TiN selectivity is listed in Table 4. [Table 4]

[0198] As shown in the results in Table 4, when the triazolium polymer was used at a concentration of 50 ppm or 70 ppm at the point of use in the two test W slurry samples, both samples provided inhibited TEOS and SiN film removal rates, significantly inhibited TiN film removal rates, and clearly increased W:TEOS, W:SiN, or W:TiN selectivities relative to the base sample without the polymer additive as a chemical additive.

[0199] Therefore, triazolium polymers can be used as very effective TiN film removal rate inhibitors in W CMP slurry applications where stopping on TiN films is required.

[0200] The effect of two different concentrations of triazolium-based polymer additives on wide-W line (50×50 μm) dishing and high density features (70% density) is listed in Table 5. [Table 5]

[0201] As shown in the results in Table 5, when the triazolium polymer was used in two test W slurry samples at a concentration of 50 ppm or 70 ppm when used, both samples provided significantly reduced wide W line dishing (more than 2-fold reduction in W line dishing) while maintaining or even reducing erosion relative to the base sample without the polymer.

[0202] Example 4 Working CMP slurries were made by adding the triazole or triazolium based polymers and copolymers made in Examples 3 and 4 above to a base CMP slurry at the time of use.

[0203] Table 6 summarizes the removal rates of tungsten (W), TEOS and SiN, as well as the W:TEOS and W:SiN selectivities. [Table 6]

[0204] Similar to Polymer 1 and Polymer 2 (as shown in Table 1), increasing concentrations of Polymer 3 and Polymer 4 inhibited their effectiveness on tungsten removal.

[0205] Similarly, as in the case of polymer 1 and polymer 2 (as shown in Table 2), polymer 3 and polymer 4 also provided high W removal rates and low TEOS and SiN removal rates, and thus high W:TEOS RR and W:SiN RR selectivities.

[0206] The dishing of wide-W line features and erosion of 70% dense features (dishing: 50 / 50 μm, erosion: 7 / 3 μm) at 20% overpolish for various formulations are summarized in Table 7. [Table 7]

[0207] As shown in Table 7, the working CMP slurries using 20 ppm of Polymer 3 and Polymer 4 showed similar reduction in 50×50 μm W line dishing and reduction in dense feature erosion as the working CMP slurries using 20 ppm of Polymer 1 and Polymer 2, as shown in Table 3.

[0208] While the principles of the present invention have been described above in connection with the preferred embodiments, it should 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 is intended to 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. 1. A chemical mechanical planarization composition comprising: 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, surface-modified inorganic oxide particles, and combinations thereof; an activator; an oxidizing agent; an additive comprising a triazole- or triazolium-based polymer or copolymer; Water, optionally A corrosion inhibitor; a dishing reducing agent; A stabilizer and A pH adjuster; Including, The triazole-based or triazolium-based polymer or copolymer is (1) having at least one triazole or triazolium group; and 【Chemical 1】 [In the formula, P １ is a polymerizable group; Sp １ is a spacer group or a single bond; R １ , R ２ are each independently selected from the group consisting of H, substituted or unsubstituted aliphatic, aromatic, heteroaromatic, and siloxane moieties, and CH is not in an aromatic or heteroaromatic ring. ２ may be replaced by O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced by F, Cl or CN; R ３ is a substituted or unsubstituted linear, cyclic or branched aliphatic group; or R ３ has formula Q, 【Chemistry 2】 [In the formula, Sp ２ is Sp １ is a spacer group which may be the same as or different from, or a single bond; selected from the group consisting of substituted or unsubstituted, linear, cyclic or branched aliphatic groups; ２ may be replaced by O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced by F, Cl or CN; P ２ Is, P １ and is a group containing a C═C double bond. X － is an anionic counterion. or formed by at least one monomer comprising a structure selected from the group consisting of （２） 【Chemistry 3】 [In the formula, L is a spacer group or a single bond; R １ , R ２ and R ３ are each independently selected from the group consisting of H or a substituted or unsubstituted aliphatic, aromatic, heteroaromatic, or siloxane moiety, with CH not being in an aromatic or heteroaromatic ring; ２ may be replaced by O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced by F, Cl or CN; n is an integer from 1 to 6000; X － is an anionic counterion. A chemical mechanical planarizing composition having a repeating unit having a structure selected from the group consisting of:

2. The polymerizable group P １ 2. The chemical mechanical planarizing composition of claim 1, wherein is selected from the group consisting of vinyl, styrene, acrylic or methacrylic, acrylamide, methacrylamide, ethylene glycol, vinyl ether, siloxane, phenol, norbornene-type backbone, and combinations thereof, preferably a group containing a C=C double bond.

3. The spacer group or single bond Sp １ or L is selected from the group consisting of substituted or unsubstituted linear, cyclic or branched aliphatic groups, CH ２ 10. The chemical mechanical planarization composition of claim 1, wherein R may be replaced with O, S, or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced with F, Cl, or CN.

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 － 10. The chemical mechanical planarizing composition of claim 1, wherein Me is selected from the group consisting of nitrates, and sulfates, and Me is methyl.

5. 10. The chemical mechanical planarizing composition of claim 1, wherein the abrasive ranges from 0.01 wt. % to 30 wt. %, from 0.05 wt. % to 20 wt. %, from 0.01 wt. % to 10 wt. %, or from 0.1 wt. % to 2 wt. %.

6. 10. The chemical mechanical planarizing composition of claim 1, wherein the additive comprising a triazole- or triazolium-based polymer or copolymer ranges from 0.00001 wt % to 1 wt %, 0.0001 wt % to 0.5 wt %, 0.0002 wt % to 0.1 wt %, or 0.0005 wt % to 0.05 wt %.

7. 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, and ferric nitrite, KClO ４ , KBrO ４ , 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 %.

8. 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) soluble catalysts selected from the group consisting of iron (III) nitrate, iron (III) ammonium oxalate trihydrate, tribasic iron (III) citrate monohydrate, iron (III) acetylacetonate, and ethylenediaminetetraacetic acid, and iron (III) sodium salt hydrate; 10. The chemical mechanical planarizing composition of claim 1, wherein the activator is selected from the group consisting of: (i) a catalyst; (ii) 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, V, and combinations thereof; and (iii) 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, V, and combinations thereof, wherein 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 %.

9. 10. The chemical mechanical planarizing composition of claim 1, 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.

10. 2. The chemical mechanical planarizing composition of claim 1, 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 %.

11. 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 without nitrogen-hydrogen bonds, sulfides, oxazolidines or mixtures of functional groups in one compound, nitrogen-containing compounds having 3 or more carbon atoms forming alkylammonium ions, aminoalkyls having 3 or more carbon atoms, at least one nitrogen-containing heterocycle or tertiary or tertiary alkyl groups.

10. The chemical mechanical planarizing composition of claim 1, wherein the dishing reducing agent is selected from the group consisting of polymeric corrosion inhibitors containing repeating groups of quaternary nitrogen atoms, polycationic amine compounds, cyclodextrin compounds, polyethyleneimine compounds, glycolic acid, chitosan, sugar alcohols, polysaccharides, alginate compounds, and sulfonic acid polymers, and combinations thereof; wherein the preferred dishing reducing agent is glycine; 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 %.

12. 10. The chemical mechanical planarizing composition of claim 1, 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 %.

13. The chemical mechanical planarizing composition of claim 1 , wherein the composition has a pH of 1-14, 1-7, 1-6, or 1.5-4.

14. The chemical mechanical planarization composition of claim 1 , wherein the abrasive is silica particles or surface-modified silica particles.

15. 2. The chemical mechanical planarizing composition of claim 1, wherein the triazole- or triazolium-based polymer or copolymer comprises at least one selected from the group consisting of poly(vinyl-4-ethyl-1,2,4-triazol-4-ium) bromide, poly(vinyl-4-ethyl-1,2,4-triazol-4-ium-co-vinylpyrrolidone) bromide, poly(vinyl-1,2,4-triazole-co-vinylpyrrolidone), and poly(vinyl-4-ethyl-1,2,4-triazol-4-ium-co-vinyl-1,2,4-triazole) bromide.

16. 2. The chemical mechanical planarizing composition of claim 1, wherein the chemical mechanical planarizing composition comprises: silica particles or surface-modified silica particles; iron(III) nitrate, malonic acid, hydrogen peroxide, a triazole- or triazolium-based polymer or copolymer comprising at least one selected from the group consisting of poly(vinyl-4-ethyl-1,2,4-triazol-4-ium) bromide, poly(vinyl-4-ethyl-1,2,4-triazol-4-ium-co-vinylpyrrolidone) bromide, poly(vinyl-1,2,4-triazole-co-vinylpyrrolidone), and poly(vinyl-4-ethyl-1,2,4-triazol-4-ium-co-vinyl-1,2,4-triazole) bromide; and water, wherein the pH of the composition is from 1.5 to 4.

17. 10. The chemical mechanical planarizing composition of claim 1, wherein the triazole-based or triazolium-based polymer or copolymer is formed by a process selected from the group consisting of free radical polymerization, reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP), atom transfer reaction polymerization (ATRP), and polycondensation reactions.

18. The chemical mechanical planarizing composition of claim 1 , wherein the triazole-based or triazolium-based copolymer has block copolymer properties.

19. 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 planarization composition according to any one of claims 1 to 18; c) polishing the at least one surface containing tungsten with the chemical mechanical planarization composition; Including, Optionally, the semiconductor substrate comprises at least one surface containing at least one of silicon nitride and silicon oxide.

20. 20. The polishing method of claim 19, wherein the at least one tungsten-containing surface comprises a dishing topography of less than 2000 angstroms or less than 1000 angstroms and an erosion topography of less than 500 angstroms.

21. The semiconductor substrate is made of silicon nitride (Si ３ N ４ or SiN), silicon oxide (SiO ２ ) and TiN, wherein the at least one surface comprises one of silicon nitride and silicon oxide, and the W to SiN removal selectivity is 100 or greater, and the W to SiO ２ 20. The polishing method of claim 19, wherein the removal selectivity of W to TiN is 60 or greater, the removal selectivity of W to TiN is 90 or greater, and the triazole-based or triazolium-based polymer or copolymer suppresses the removal rate of TiN.

22. 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 according to any one of claims 1 to 18; Equipped with The at least one tungsten-containing surface is in contact with the polishing pad and the chemical mechanical planarizing composition, thereby polishing the at least one tungsten-containing surface with the chemical mechanical planarizing composition.

23. 23. The system for chemical mechanical planarization of a semiconductor substrate having at least one surface containing tungsten as recited in claim 22, wherein the at least one surface containing tungsten comprises a dishing topography of less than 2000 angstroms or less than 1000 angstroms and an erosion topography of less than 500 angstroms.

24. The semiconductor substrate is made of silicon nitride (Si ３ N ４ or SiN), silicon oxide (SiO ２ ), and at least one surface containing TiN, wherein the removal selectivity of W to SiN is 100 or greater, and W to SiO ２ 23. The system for chemical mechanical planarization of a semiconductor substrate having at least one surface containing tungsten of claim 22, wherein the removal selectivity of W to TiN is 60 or greater and the removal selectivity of W to TiN is 90 or greater, and the triazole-based or triazolium-based polymer or copolymer suppresses the removal rate of TiN.

25. having at least one triazole or triazolium group; 【Chemistry 4】 [In the formula, P １ is a polymerizable group; Sp １ is a spacer group or a single bond; R １ , R ２ are each independently selected from the group consisting of H, a substituted or unsubstituted aliphatic, aromatic, heteroaromatic, or siloxane moiety, and CH is not in an aromatic or heteroaromatic ring. ２ may be replaced by O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced by F, Cl or CN; R ３ is a substituted or unsubstituted linear, cyclic or branched aliphatic group; or R ３ has formula Q, 【Chemistry 5】 [In the formula, Sp ２ is Sp １ is a spacer group which may be the same as or different from, or a single bond; selected from the group consisting of substituted or unsubstituted, linear, cyclic or branched aliphatic groups; ２ may be replaced by O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced by F, Cl or CN; P ２ Is, P １ and is a group containing a C═C double bond. X － is an anionic counterion.

1. A triazole- or triazolium-based polymer or copolymer formed by at least one monomer comprising a structure selected from the group consisting of:

26. [Chemical 6] [In the formula, L is a spacer group or a single bond; R １ , R ２ and R ３ are each independently selected from the group consisting of H or a substituted or unsubstituted aliphatic, aromatic, heteroaromatic, or siloxane moiety, with CH not being in an aromatic or heteroaromatic ring; ２ may be replaced by O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced by F, Cl or CN; n is an integer from 1 to 6000; X － is an anionic counterion.

1. A triazole- or triazolium-based polymer or copolymer comprising at least one repeat unit having a structure selected from the group consisting of:

27. The polymerizable group P １ is selected from the group consisting of vinyl, styrene, acrylic or methacrylic, acrylamide, methacrylamide, ethylene glycol, vinyl ether, siloxane, phenol, norbornene-type backbone, and combinations thereof, preferably a group containing a C=C double bond.

28. The spacer group or the single bond Sp １ or L is selected from the group consisting of substituted or unsubstituted, linear, cyclic or branched aliphatic groups, CH ２ may be replaced by O, S or N so that the heteroatoms are not bonded to each other, and hydrogen may be replaced by F, Cl or CN.

29. 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 － 27. The triazole or triazolium based polymer or copolymer of claim 25 or 26, wherein the triazole or triazolium based polymer or copolymer is selected from the group consisting of nitrates, and sulfates.

30. 27. The triazole- or triazolium-based polymer or copolymer of claim 25 or 26, wherein the triazole- or triazolium-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.

31. 27. The triazole- or triazolium-based polymer or copolymer of claim 25 or 26, wherein the copolymer has block copolymer properties.

32. 27. The triazole- or triazolium-based polymer or copolymer of claim 25 or 26, selected from the group consisting of poly(vinyl-4-ethyl-1,2,4-triazol-4-ium) bromide; poly(vinyl-4-ethyl-1,2,4-triazol-4-ium-co-vinylpyrrolidone) bromide; poly(vinyl-1,2,4-triazole-co-vinylpyrrolidone); and poly(vinyl-4-ethyl-1,2,4-triazol-4-ium-co-vinyl-1,2,4-triazole) bromide.

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