Environmentally friendly biocides for chemical mechanical planarization (cmp) polishing compositions

Abstract

The present invention provides environmentally friendly biocides for inhibiting the growth of microorganisms (bacterial and / or fungal growth) in chemical mechanical planarization (CMP) polishing compositions.

Description

Cross-referencing of related patent applications

[0001] This application claims the benefit of U.S. Application No. 63 / 601,467, filed November 21, 2023. The disclosure of that application is incorporated herein by reference. Background Technology

[0002] This invention relates to chemical mechanical planarization (CMP) polishing compositions. More specifically, this invention relates to protecting chemical mechanical planarization (CMP) polishing compositions using environmentally friendly biocides that inhibit the growth of microorganisms (bacteria and / or fungi) in the composition.

[0003] The problem of bacterial and fungal growth in polishing compositions is known in the art.

[0004] US3,336,236 addresses this issue using sodium chlorite in sufficient amounts to inhibit bacterial growth and reproduction; US3,816,330 addresses it using hexachlorophenol at approximately 10-1000 ppm; US3,860,431 and US2,823,186 address it using polyols; US2,801,216 and 3,046,234 address it using dialdehydes; US3,377,275 and 3,148,110 address it using formaldehyde; however, the above methods result in unacceptable polishing rates. Therefore, US4,169,337; US4,462,188; US4,588,421; and US4,892,612 teach the use of various polishing rate enhancers to increase polishing rates.

[0005] US5,230,833 found that increased microbial growth was observed during the recycling and dilution of slurries that did not exhibit microbial growth. Microbial growth was promoted when an organic rate accelerator was used.

[0006] US 5,230,833 addresses this problem using bactericides and fungicides, such as tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, alkylbenzyldimethylammonium chloride, and alkylbenzyldimethylammonium hydroxide, wherein the alkyl chain ranges from 1 to about 20 carbon atoms. Preferred biocides are sodium chlorite or sodium hypochlorite; and preferred fungicides are OMADINE® (pyrithione) sodium.

[0007] WO200160940 states that the aforementioned chemicals used to inhibit microbial growth are not always compatible with abrasive slurries used in chemical-mechanical polishing (CMP) of semiconductor wafers and with non-abrasive slurries (which are used with fixed abrasive polishing pads for semiconductor wafer polishing). WO200160940 discloses the use of five-membered organic ring compounds containing both sulfur and nitrogen in the ring, which provide biocidal protection to CMP slurries without affecting polishing performance. Examples of such compounds are 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT) and 2-methyl-4-isothiazolin-3-one (MIT), which have been widely adapted for use as biocides. US8,999,193 discloses the use of MIP and CMIP as biocides in tungsten CMP polishing compositions; US10,600,655 discloses the use of MIP and CMIP as biocides in STI CMP polishing compositions; and US11,718,767 discloses the use of MIP and CMIP as biocides in SiN CMP polishing compositions.

[0008] Commonly used biocides in CMP polishing compositions contain 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2-methyl-4-isothiazolin-3-one (MIT), or 2-n-octyl-4-isothiazolin-3-one (OIT).

[0009] However, heterocyclic organic compounds are known to be harmful to the environment: wastewater treatment systems, human health, high toxicity to aquatic life, and worst of all, persistent effects.

[0010] In addition, CMP compositions require growth inhibitors or preservatives to prevent the growth of microorganisms (bacteria and fungi) during storage.

[0011] It should be obvious from the above that there remains a high demand in the field for environmentally friendly or eco-friendly chemicals as alternative biocides in CMP polishing compositions, especially during storage. Summary of the Invention

[0012] This invention addresses the need by providing ideal environmentally friendly or eco-friendly chemicals as alternative biocides to replace commonly used MIP, CMIP, and OIT biocides in CMP polishing compositions.

[0013] More specifically, this invention discloses the use of FDA-approved food preservatives and additives as effective biocides in CMP polishing compositions.

[0014] In one aspect (Aspect 1), a CMP polishing composition is provided, comprising, substantially comprising, or comprising the following substances: Chemical additives; biocides; and Water-soluble solvents; and Optionally at least one of the following: Abrasives; pH adjuster; Oxidizing agent; Activator; Surfactants; Corrosion inhibitors; The pH of the composition is in the range of 2 to 9, 2 to 8, 2 to 7, or 2 to 6.

[0015] Chemical additives can be any additive that promotes microbial growth in the CMP polishing composition. Chemical additives include, but are not limited to, any chemical that functions in the CMP polishing composition as a pit reducer, removal rate inhibitor, removal rate promoter, surfactant, corrosion inhibitor, erosion reducer, defect reducer, dispersant, chelating agent, stabilizer, or combination thereof. These functions have their meanings generally acceptable in the art and should be readily understood by one of ordinary skill in the art. For example, pit reducers reduce pitting during polishing; organic rate promoters / inhibitors enhance / inhibit the polishing rate of the material being polished.

[0016] Biocides are environmentally friendly chemicals, including but not limited to FDA-approved food additives and / or preservatives. For example, biocides include, but are not limited to, sorbic acid, its derivatives, or salts thereof; and benzoic acid, its derivatives, or salts thereof.

[0017] Optional abrasives include, but are not limited to, inorganic oxide particles, inorganic oxide particles coated with metal oxides, organic polymer particles, organic polymer particles coated with metal oxides, and combinations thereof.

[0018] Optional pH adjusters include, but are not limited to (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 pH; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine and mixtures thereof for raising pH.

[0019] Optional oxidizing agents include, but are not limited to, peroxides selected from hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, peroxypropionic acid, substituted or unsubstituted peroxybutyric acid, hydroperoxyacetaldehyde, potassium periodate and ammonium peroxymonosulfate; and non-peroxides selected from ferrous nitrite, KClO4, KBrO4 and KMnO4; and combinations thereof.

[0020] Optional activators include, but are not limited to: (1) inorganic oxide particles coated on the surface of a transition metal, wherein the transition metal is selected from Fe, Cu, Mn, Co, Ce and combinations thereof; (2) soluble catalysts selected from ferric nitrate (III), ferric oxalate (III) ammonium trihydrate, ferric citrate (III) monohydrate, acetylacetone iron (III), ethylenediaminetetraacetic acid, ferric (III) sodium salt hydrate and combinations thereof; (3) metal compounds having multiple oxidation states selected from Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V and combinations thereof; and combinations thereof.

[0021] The optional surfactant can be any surfactant, including but not limited to nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof.

[0022] The optional corrosion inhibitor can be any corrosion inhibitor, including but not limited to nitrogen-containing cyclic compounds.

[0023] In another aspect (Aspect 2), a CMP polishing method for chemical mechanical planarization of a semiconductor substrate is provided, the semiconductor substrate comprising at least one surface containing at least one material, the method comprising the following steps: Make at least one surface contact the polishing pad; Delivery aspect 1: CMP polishing composition; The at least one surface containing at least one material is polished with a CMP polishing composition.

[0024] In another aspect (aspect 3), a CMP polishing system is provided, comprising: A semiconductor substrate, comprising at least one surface containing at least one material; Polishing pads; and CMP polishing composition of aspect 1; The at least one surface containing at least one material is in contact with the polishing pad and the CMP polishing composition.

[0025] At least one material means any material used in a semiconductor substrate or patterned wafer; including metals or metal alloys such as W, Cu, Co, Al, Ni, Mn and their alloys; new metals such as Ru; barrier layer materials such as Ta, TaN, Ti, TiN and Co; dielectric materials such as SiO2, SiN and SiC; and low-k and ultra-low-k materials such as black diamond.

[0026] Other aspects, features, and embodiments of the invention will become more apparent from the following disclosure and the appended claims.

[0027] The embodiments of the present invention can be used individually or in combination with each other. Detailed Implementation

[0028] The purpose of this invention is to provide an environmentally friendly biocide.

[0029] This invention addresses the need by providing ideal environmentally friendly or eco-friendly chemicals as components in CMP polishing compositions; and by providing alternative biocides in systems and methods for using CMP polishing compositions or slurries. The CMP polishing compositions or CMP polishing slurries are interchangeable.

[0030] More specifically, this invention discloses an environmentally friendly biocide that inhibits microbial growth in CMP polishing compositions containing chemical additives that promote microbial growth. Environmentally friendly biocides include, but are not limited to, certain FDA-approved food additives and preservatives.

[0031] CMP polishing compositions can be abrasive-free CMP polishing compositions used together with fixed abrasive polishing pads for polishing semiconductor wafers.

[0032] CMP polishing compositions may also contain more than one part, such as two parts: a chemical package and an abrasive package, where the two packages are mixed together during use. The chemical package typically contains chemical additives that promote microbial growth, and therefore often contains biocides. The package may also be concentrated and diluted before use. The abrasive package typically also contains biocides to prevent microbial growth, thereby extending its shelf life.

[0033] In one aspect (Aspect 1), a CMP polishing composition is provided, comprising, substantially comprising, or comprising the following substances: Chemical additives; biocides; and Water-soluble solvents; and Optionally at least one of the following: Abrasives; pH adjuster; Oxidizing agent; Activator; Surfactants; Corrosion inhibitors; The pH of the composition is in the range of 2 to 9, 2 to 8, 2 to 7, or 2 to 6.

[0034] Chemical additives can be any additive that promotes microbial growth in the CMP polishing composition. Chemical additives include, but are not limited to, any chemical that functions in the CMP polishing composition as a pit reducer, removal rate inhibitor, removal rate promoter, surfactant, corrosion inhibitor, erosion reducer, defect reducer, dispersant, chelating agent, stabilizer, or combination thereof. These functions have their meanings generally acceptable in the art and should be readily understood by one of ordinary skill in the art. For example, pit reducers reduce pitting during polishing; organic rate promoters / inhibitors enhance / inhibit the polishing rate of the material being polished.

[0035] For example, chemical additives can be depression reducing agents, such as (a) polyols, including but not limited to maltitol, lactitol, maltotriol, ribitol, D-sorbitol, mannitol, eugenol, idoteol, D-(-)-fructose, anhydrous sorbitol, sucrose, ribose, inositol, glucose, D-arabinose, L-arabinose, D-mannose, L-mannose, mesoerythritol, β-lactose, arabinose, fructose, xylitol, and combinations thereof, such as US The following are disclosed in US11,078,417 regarding STI polishing compositions: (b) 1,8-diazabicyclo(5.4.0) undec-7-ene (DBU) and / or 2-aminobenzimidazole for W polishing compositions as disclosed in US20200040256; and (c) 1,2,4-triazole, 1,2,3-triazole and benzotriazole for Cu polishing compositions as disclosed in US11,401,441.

[0036] Chemical additives may also be removal rate promoters, such as (a) organic sulfonic acids, organic aromatic sulfonic acids such as benzenesulfonic acid, piperazine, and organic phosphonic acids used in STI polishing compositions disclosed in US 2020004,551; (b) organic carboxylic acids used in W polishing compositions disclosed in US 20200040256; and (c) various amino acids (such as glycine and alanine), amino acid derivatives, and organic amines used in Cu polishing compositions disclosed in US 9,978,609.

[0037] Chemical additives can also be polymers or copolymers, including but not limited to polyacrylic acid, polymethacrylic acid, polyamide, polystyrene sulfonic acid, polyamine, polyethyleneimine, polyethylene oxide, polypropylene oxide, polyethylene glycol, polyglycerol, polyoxyethylene, polyglycerol ether, polyoxypropylene, polyglycerol ether, polyacrylamide, poly(acrylic acid-co-maleic acid), poly(acrylamide-co-acrylic acid), poly(methyl vinyl ether), poly(propylene glycol), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate), polyvinylsulfonic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyridine-N- Oxides, poly(acrylamide-acrylic acid), poly(4-styrenesulfonic acid-co-maleic acid), polyacrylamide-co-diallyldimethylammonium chloride, poly(ethylene-co-methacrylic acid) and polyethylene ether, poly(4-vinylpyridine), poly(4-vinylpyridine-co-butyl methacrylate), poly(diallyldimethylammonium chloride), poly(N-isopropylacrylamide), poly(vinylphosphonic acid), polyethylene glycol, polyoxyethylene sorbitan tetraoleate, polysorbate 20, polysorbate 40, polysorbate 80, poly(vinyl acetate), poly(styrene-co-allyl alcohol), poly(4-vinylphenol), and poly(2-ethyl-2-oxazoline).

[0038] The concentration (or amount) of the chemical additive is in the range of 0.01% by weight to 20.0% by weight, 0.05% by weight to 15% by weight, or 0.1% by weight to 10% by weight. Weight percentages are relative to the composition.

[0039] Biocides are environmentally friendly chemicals, including but not limited to FDA-approved food additives and / or preservatives. For example, biocides include, but are not limited to, sorbic acid, its derivatives, or salts thereof; and benzoic acid, its derivatives, or salts thereof.

[0040] Benzoic acid, its derivatives and their salts, including but not limited to those having the following general molecular structures: (a) (b) and their combinations.

[0041] R1, R2, R3, R4 and R5 are each independently selected from hydrogen, hydroxyl, alkyl, alkoxy, amino, dialkylamino, alkylthio, and combinations thereof.

[0042] R1, R2, R3, R4, and R5 can all be hydrogen atoms, yielding benzoic acid or its salts. Some of R1, R2, R3, R4, and R5 can be hydrogen atoms, and others can be different functional groups attached to the -2, -3, -4, -5, or -6 positions of the benzoic acid derivative. These functional groups include, but are not limited to, hydroxyl, alkyl, alkoxy, amino, dialkylamino, and alkylthio groups. These functional groups can be attached to the benzoic acid ring in a mono-, di-, or tri-form.

[0043] M + It is a metal ion, including but not limited to potassium ions, ammonium ions, and sodium ions. Potassium salts and ammonium salts of benzoic acid are preferred.

[0044] Examples of benzoic acid and its derivatives have the following molecular structures:

[0045] The structures are benzoic acid (a), 2-hydroxybenzoic acid (salicylic acid) (b), 3-hydroxybenzoic acid (c), 4-hydroxybenzoic acid (d), 3,4-dihydroxybenzoic acid (e), 3,4,5-trihydroxybenzoic acid (f), 3-methoxy-4-hydroxybenzoic acid (g), 4-methoxybenzoic acid (h), 4-methylbenzoic acid (i), 2,6-dimethoxy-4-hydroxybenzoic acid (j), 3,5-dimethoxy-4-hydroxybenzoic acid (k), and 2,3-dihydroxybenzoic acid. (l), 2,4-dihydroxybenzoic acid (m), 2,5-dihydroxybenzoic acid (n), 2,6-dihydroxybenzoic acid (o), 3,5-dihydroxybenzoic acid (p), 2,4,6-trihydroxybenzoic acid (q), 4-(dimethylamino)benzoic acid (r), 3,5-diaminobenzoic acid (s), 2-methoxybenzoic acid (t), 2-ethoxybenzoic acid (u), 2-aminobenzoic acid (v), 3-methylthiabenzoic acid (w) and 4-methylthiabenzoic acid (x).

[0046] Biocides can also be sorbic acid, its derivatives and their salts, such as potassium salt of sorbic acid, ammonium salt of sorbic acid, sodium salt of sorbic acid, sorbohydroxamic acid and sorbal.

[0047] The amount of biocide can range from about 0.005% by weight to 1.0% by weight, about 0.01% by weight to 0.75% by weight, or about 0.05% by weight to 0.5% by weight. Weight percentages are relative to the composition.

[0048] Water-soluble solvents include, but are not limited to, deionized (DI) water, distilled water, and alcoholic organic solvents.

[0049] The optional abrasives include, but are not limited to, inorganic oxide particles, including but not limited to pyrolytic silica, colloidal silica, high-purity colloidal silica, pyrolytic alumina, colloidal alumina, cerium oxide, titanium dioxide, and zirconium oxide; inorganic oxide particles coated with metal oxides, including but not limited to cerium oxide-coated inorganic oxide particles; organic polymer particles; organic polymer particles coated with metal oxides; and combinations thereof.

[0050] The amount of abrasive can range from about 0.01% to 30% by weight, about 0.05% to 20% by weight, about 0.01% to 10% by weight, or about 0.1% to 5% by weight. Weight percentages are relative to the composition.

[0051] The average particle size of the abrasive particles (measured by dynamic light scattering DLS technology) is approximately 2 nm to 1,000 nm, 10 nm to 500 nm, or 20 nm to 250 nm; or 2 nm to 160 nm, 2 nm to 100 nm, 2 nm to 80 nm, 2 nm to 60 nm, 3 nm to 50 nm, 3 nm to 40 nm, 4 nm to 30 nm, or 5 nm to 20 nm.

[0052] Optional oxidizing agents include, but are not limited to, peroxide compounds selected from hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, peroxypropionic acid, substituted or unsubstituted peroxybutyric acid, hydroperoxyacetaldehyde, potassium periodate and ammonium peroxymonosulfate; and non-peroxide compounds selected from ferrous nitrite, KClO4, KBrO4 and KMnO4; and combinations thereof.

[0053] The amount of oxidant can range from about 0.01% by weight to 30% by weight, from about 0.1% by weight to 20% by weight, or from about 0.5% by weight to about 10% by weight. Weight percentages are relative to the composition.

[0054] Optional activators include, but are not limited to: (1) inorganic oxide particles coated on the surface of a transition metal, wherein the transition metal is selected from Fe, Cu, Mn, Co, Ce and combinations thereof; (2) soluble catalysts selected from ferric nitrate (III), ferric oxalate (III) ammonium trihydrate, ferric citrate (III) monohydrate, acetylacetone iron (III), ethylenediaminetetraacetic acid, ferric (III) sodium salt hydrate and combinations thereof; (3) metal compounds having multiple oxidation states selected from Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V and combinations thereof; and combinations thereof.

[0055] The amount of activator can be in the range of about 0.00001 wt% to 5 wt%, about 0.0001 wt% to 2.0 wt%, about 0.0005 wt% to 1.0 wt%; or about 0.001 wt% to 0.5 wt%.

[0056] The optional surfactant can be any surfactant, including but not limited to nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof.

[0057] Nonionic surfactants can be selected from a range of chemical types, including but not limited to long-chain alcohols, ethoxylated alcohols, ethoxylated acetylsyl glycol surfactants, polyethylene glycol alkyl ethers, propylene glycol alkyl ethers, glucoside alkyl ethers, polyethylene glycol octylphenyl ethers, polyethylene glycol alkylphenyl ethers, glyceryl alkyl esters, polyoxyethylene glycol dehydrated sorbitol alkyl esters, dehydrated sorbitol alkyl esters, cocamidoyl monoethanolamine, cocamidoyl diethanolamine, dodecyl dimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amine, and fluorinated surfactants. The polymer molecular weight of the surfactants can range from several hundred to over one million. These materials also exhibit a wide viscosity distribution.

[0058] Anionic surfactants include, but are not limited to, salts with suitable hydrophobic tails, such as alkyl carboxylates, alkyl polyacrylates, alkyl sulfates, alkyl phosphates, alkyl dicarboxylates, alkyl hydrogen sulfates, and alkyl diphosphates; as well as substituted aryl carboxylates, substituted aryl sulfates, substituted aryl phosphates, substituted aryl dicarboxylates, substituted aryl hydrogen sulfates, and substituted aryl diphosphates. The counterions of these surfactants include, but are not limited to, potassium, ammonium, and other positive ions. The molecular weights of these anionic wetting agents range from several hundred to several hundred thousand.

[0059] Cationic surfactants have a net positive charge on the major parts of their molecular framework. Cationic surfactants are typically halides of molecules that contain hydrophobic chains and cationic charge centers such as amines, quaternary ammonium, benzyl ammonium, and alkylpyridinium ions.

[0060] On the other hand, surfactants can be amphoteric surfactants, which have positive (cationic) and negative (anionic) charges on their main molecular chains and possess their opposing ions. The cationic moiety is based on a primary, secondary, or tertiary amine or a quaternary ammonium cation. The anionic moiety can be more variable and includes sulfonate groups, such as in sulfobetaine CHAPS (3-[(3-cholamidopropyl)dimethylammonium]-1-propanesulfonic acid) and cocamidopropyl hydroxysulfobetaine. Betaines, such as cocamidopropyl betaine, have a carboxylate group with ammonium. Some amphoteric surfactants can have phosphate anions with amine or ammonium, such as phospholipids like phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelin.

[0061] The amount of surfactant can range from 0.0001 wt% to 10 wt%, 0.01 wt% to 3 wt%, or 0.05 wt% to 1 wt%.

[0062] Optional corrosion inhibitors can be any corrosion inhibitor, including but not limited to nitrogen-containing cyclic compounds; such as 1,2,3-triazole, 1,2,4-triazole, 1,2,3-benzotriazole, 5-methylbenzotriazole, benzotriazole, 1-hydroxybenzotriazole, 4-hydroxybenzotriazole, 3-amino-1,2,4-triazole, 4-amino-4H-1,2,4-triazole, 5-aminotriazole, benzimidazole, benzothiazoles such as 2,1,3-benzothiadiazole, triazine thiols, triazine dithiols and triazine trithiols, pyrazoles, imidazoles, isocyanurates such as 1,3,5-tris(2-hydroxyethyl) isocyanuric acid, and mixtures thereof. Preferred inhibitors are 1,2,4-triazole, 5-aminotriazole, and 1,3,5-tris(2-hydroxyethyl) isocyanurate.

[0063] The amount of corrosion inhibitor can be less than 1.0% by weight, less than 0.5% by weight, or less than 0.25% by weight.

[0064] In another aspect (Aspect 2), a CMP polishing method for chemical mechanical planarization of a semiconductor substrate is provided, the semiconductor substrate comprising at least one surface containing at least one material, the method comprising the following steps: Make at least one surface contact the polishing pad; Delivery aspect 1: CMP polishing composition; The at least one surface containing at least one material is polished with a CMP polishing composition.

[0065] In another aspect (aspect 3), a CMP polishing system is provided, comprising: A semiconductor substrate, comprising at least one surface containing at least one material; Polishing pads; and CMP polishing composition of aspect 1; At least one of the surfaces containing at least one material is in contact with the polishing pad and the CMP polishing composition.

[0066] At least one material means any material used in a semiconductor substrate or patterned wafer; including metals or metal alloys such as W, Cu, Co, Al, Ni, Mn and their alloys; new metals such as Ru; barrier layer materials such as Ta, TaN, Ti and TiN; dielectric materials such as SiO2, SiN and SiC; and low-k and ultra-low-k materials such as black diamond.

[0067] The following non-limiting embodiments are provided to further illustrate the invention.

[0068] Biocidal efficacy test The cerium dioxide-coated silica particles have an average particle size (MPS) or primary particle size (measured by DLS) of 20 nanometers (nm) to 500 nanometers (nm) (provided by JGCC Inc., Japan).

[0069] Chemicals such as D-sorbitol, sorbic acid, benzoic acid, and all other chemical raw materials are supplied by Millipore Sigma, St. Louis, MO.

[0070] D-sorbitol is used as a chemical additive to prepare abrasive-free CMP polishing compositions, or as a chemical packaging composition in dual-package CMP polishing compositions.

[0071] Biocidal efficacy tests were conducted with the intentional addition of microorganisms (bacteria and fungi). All tests were performed at 30°C.

[0072] Example 1 The reference sample (Ref.) contained 15% by weight of D-sorbitol, pH adjuster, and deionized water.

[0073] All working samples (WS) contained 15% by weight of D-sorbitol, pH adjuster, and deionized water, as well as benzoic acid or one of its derivatives.

[0074] WS #1 contains 0.1 wt% benzoic acid (a), WS #2 contains 0.1 wt% 4-hydroxybenzoic acid (d), WS #3 contains 0.1 wt% 3,4,5-trihydroxybenzoic acid (f), WS #4 contains 0.1 wt% 4-hydroxy-3-methoxybenzoic acid (g), WS #5 contains 0.1 wt% 4-methoxybenzoic acid (h), WS #6 contains 0.1 wt% 4-methylbenzoic acid (i), WS #7 contains 0.1 wt% 2,3-dihydroxybenzoic acid (l), and WS #8 contains 0.1 wt% 3,5-diaminobenzoic acid (s), which are used as biocides. All working samples were adjusted to pH 2.15.

[0075] The test results are listed in Table 1 below.

[0076] Table 1. Comparison of biocidal efficacy test results

[0077] Colony forming units / mL (cfu / ml) As shown in Table 1, the test results indicate that the reference contaminant reading on day 7 was higher than that on day 0 (0), suggesting microbial growth in the absence of biocides.

[0078] All working samples showed significantly lower contaminant readings on day 7 than on day 0. Therefore, benzoic acid and its derivatives demonstrate the ability to prevent microbial growth in the composition.

[0079] Example 2 To evaluate the effect of benzoic acid concentration on the efficacy of biocides.

[0080] All compositions contain 15% by weight of D-sorbitol, deionized water, and a pH adjuster. The compositions are adjusted to a highly acidic pH of approximately 2.1.

[0081] Three working samples, 9 (WS #9), 10 (WS #10) and 11 (WS #11), were prepared with benzoic acid at concentrations of 0.001 wt%, 0.01 wt%, and 0.1 wt%, respectively.

[0082] The test results are listed in Table 2 below.

[0083] Table 2. Benzoic acid concentration test

[0084] The 0.001% by weight of benzoic acid (WS #9) in the composition is not effective in preventing the growth of microorganisms in the composition.

[0085] The contaminant readings of WS #10 and WS #11 on day 7 were significantly lower than those on day 0. The use of 0.01 and 0.1% by weight of benzoic acid in the composition effectively prevented microbial growth.

[0086] Example 3 In this embodiment, all compositions contain 15% by weight D-sorbitol, 0.1% by weight sorbic acid, a pH adjuster, and deionized water. Sorbic acid is used as an alternative biocide.

[0087] The pH of Working Example 12 (WS #12) was adjusted to 4.0.

[0088] The pH of Working Example 13 (WS #13) was adjusted to 5.0.

[0089] The results of the biocidal efficacy test are listed in Table 3.

[0090] Table 3. Results of biocidal efficacy test for sorbic acid concentration

[0091] As shown in Table 3, the test results indicate that 0.1% by weight of sorbic acid exhibits highly effective biocidal efficacy at pH 4.0 and 5.0 to prevent bacterial growth.

[0092] Polishing experiment parameter: A: Antelope - a unit of length BP: Back pressure, measured in psi CMP: Chemical Mechanical Planarization = Chemical Mechanical Polishing CS: Carrier speed DF: Downforce: The pressure applied during CMP, in psi. min: minutes ml: milliliters mV: millivolt psi: pounds per square inch PS: The platform rotation speed of the polishing equipment is measured in rpm (revolutions per minute). SF: Polishing composition flow rate, ml / min TEC: Silicon oxide film produced by chemical vapor deposition (CVD) using tetraethyl orthosilicate as a precursor. Wt.%: (Weight percentage of the listed components) Removal rate (RR) = (film thickness before polishing - film thickness after polishing) / polishing time.

[0093] Removal rate and selectivity Tungsten removal rate: Tungsten removal rate measured at 2.5 psi pressure in a CMP device.

[0094] TEOS removal rate: The TEOS removal rate measured at a given downpressure. The downpressure for the CMP equipment is 2.5 psi.

[0095] SiN removal rate: The SiN removal rate measured at a given pressure. The pressure of the CMP equipment is 2.5 psi.

[0096] Polishing pads IC1010 and other pads, supplied by DOW, Inc., are used during CMP.

[0097] Metrology The film was measured using a ResMap CDE, model 168, manufactured by Creative Design Engineering, Inc., 20565 Alves Dr., Cupertino, CA 95014. The ResMap device is a four-point probe thin-film resistance device. A 49-point diameter scan with 5 mm edge exclusion was performed on the film.

[0098] CMP equipment The CMP equipment used was a 200mm Mirra or 300mm Reflexion manufactured by Applied Materials, 3050 Boweres Avenue, Santa Clara, California, 95054. IC1010 pads supplied by DOW, Inc., 451 Bellevue Rd., Newark, DE 19713 were used on stage 1 for blanket-covered and patterned wafer studies.

[0099] Run in the IC1010 pad or other pads by dressing them on a dresser with a downforce of 7 pounds for 18 minutes. To ensure proper device setup and pad run-in, polish four TEOS monitoring pads under baseline conditions using a Versum® STI 2305 composition (supplied by Versum Materials Inc.).

[0100] Chips Polishing experiments were conducted using PECVD, LECVD, or HD TEOS wafers and SiN wafers. The patterned wafers were MIT864 oxide patterned wafers. These blanket-coated and patterned wafers were purchased from Silicon Valley Microelectronics, 2985 Kifer Rd., Santa Clara, CA 95051.

[0101] In the study of blanket-coated wafers, oxide blanket-coated wafers and SIN blanket-coated wafers were polished under baseline conditions. The baseline equipment conditions were: stage speed: 87 rpm, head speed: 93 rpm, membrane pressure: 3.1 psi, composition flow rate: 200 ml / min; 100% in-situ finishing was performed using a Saesol E4 disc.

[0102] These polished patterned wafers were measured on a Veeco VX 300 profilometer / AFM instrument (MIT 864).

[0103] Example 4 In CMP polishing Example 4, the removal rate of different films was measured and the RR selectivity was calculated.

[0104] Reference polishing composition 1 (Reference 1) contains 0.5 wt% cerium dioxide-coated silica abrasive, 0.15 wt% D-sorbitol, 18.6 ppm bioban 425 (2-octyl-2H-isothiazolinone, OIT biocide) as a biocide, a pH adjuster, and deionized water. The pH is adjusted to 5.35.

[0105] Reference polishing composition 2 (Reference 2) contains 0.5% by weight of cerium dioxide-coated silica abrasive, 0.15% by weight of D-sorbitol, a pH adjuster, deionized water, and is free of biocides. The pH is adjusted to 5.35.

[0106] The working polishing composition (working sample) contains 0.5 wt% cerium dioxide-coated silica abrasive, 0.15 wt% D-sorbitol, 10.0 ppm benzoic acid as an environmentally friendly biocide, a pH adjuster, and deionized water. The pH is adjusted to 5.35.

[0107] The results of blanket-coated film polishing are shown in Table 4.

[0108] Table 4. Effects of environmentally friendly biocides on the selectivity of membrane RR & oxide:SiN

[0109] As shown in Table 4, the CMP polishing performance was almost identical among the three polishing compositions.

[0110] Furthermore, the use of biocides (environmentally friendly biocides or conventional OIT biocides) in the polishing composition does not affect CMP polishing performance.

[0111] Example 5 In CMP polishing Example 5, oxide trench spacing recesses of different dimensions were obtained from two reference samples and a working sample, with different overpolishing times. The results are listed in Table 5.

[0112] Table 5. Effect of environmentally friendly biocides on oxide trench depression vs. OP time (seconds)

[0113] As shown in Table 5, when the environmentally friendly biocide benzoic acid was used instead of the traditional OIT biocide, similar oxide trench depressions were obtained on two different sized features versus different overpolishing times.

[0114] The polishing results of oxide patterned wafers obtained by two reference samples and working samples at different size features were compared and are listed in Table 6.

[0115] Table 6. Effect of environmentally friendly bactericides on the sinking rate of oxidation trenches

[0116] As shown in Table 6, when the environmentally friendly biocide benzoic acid is used instead of the traditional OIT biocide, similar or slightly lower oxide trench indentation rates are obtained on oxide trench features of different sizes relative to oxide trench indentation rates on 100 μm or 200 μm features.

[0117] As shown in the results above, the disclosed environmentally friendly biocide has demonstrated the same CMP polishing performance as conventionally used biocides.

[0118] The embodiments of the invention listed above, including working examples, are examples of many embodiments that can be constructed from the invention. Many other configurations of the method are contemplated, and the materials used in the method can be selected from many materials other than those specifically disclosed.

Claims

1. A chemical mechanical planar polishing composition comprising, substantially consisting of, or consisting of the following substances: Chemical additives; biocides; and Water-soluble solvents; and Optionally at least one of the following: Abrasives; pH adjuster; Oxidizing agent; Activator; Surfactants; Corrosion inhibitors; in The biocide is selected from sorbic acid, its derivatives or salts thereof; benzoic acid, its derivatives or salts thereof; and combinations thereof; and The pH of the composition is in the range of 2 to 9, 2 to 8, 2 to 7, or 2 to 6.

2. The chemimechanical planarization polishing composition according to claim 1, wherein the chemical additive promotes the growth of microorganisms in the polishing composition.

3. The chemimechanical planar polishing composition according to any one of claims 1 to 2, wherein the chemical additive is selected from (a) maltitol, lactitol, maltotriol, ribitol, D-sorbitol, mannitol, eurythritol, idutitol, D-(-)-fructose, anhydrous sorbitol, sucrose, ribose, inositol, glucose, D-arabinose, L-arabinose, D-mannose, L-mannose, mesoerythritol, β-lactose, arabinose, fructose, xylitol, and combinations thereof; (b) 2-aminobenzimidazole, 1,8-diazazolium (c) Bicyclic (5.4.0) undec-7-ene and combinations thereof; (d) organic sulfonic acids, organic aromatic sulfonic acids, piperazines, organic phosphonic acids and combinations thereof; (e) organic carboxylic acids; (f) amino acids or amines; (c) selected from polyacrylic acid, polymethacrylic acid, polyamide, polystyrene sulfonic acid, polyamine, polyethyleneimine, polyethylene oxide, polypropylene oxide, polyethylene glycol, polyglycerol, polyoxyethylene, polyglycerol ether, polyoxypropylene, polyglycerol ether, polyacrylamide, poly(acrylic acid-co-maleic acid), poly(acrylamide-co-acrylic acid), poly(methyl vinyl ether), poly( Propylene glycol), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate), polyvinylsulfonic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyridine-N-oxide, poly(acrylamide-acrylic acid), poly(4-styrenesulfonic acid-co-maleic acid), polyacrylamide-co-diallyldimethylammonium chloride, poly(ethylene-co-methacrylic acid) and polyvinyl ether, poly(4-vinylpyridine), poly(4-vinylpyridine-co-butylmethyl methacrylate) Polymers or copolymers thereof, including (a) to (g) acrylates, poly(diallyldimethylammonium chloride), poly(N-isopropylacrylamide), poly(vinylphosphonic acid), polyethylene glycol, polyoxyethylene sorbitan tetraoleate, polysorbate 20, polysorbate 40, polysorbate 80, poly(vinyl acetate), poly(styrene-co-allyl alcohol), poly(4-vinylphenol) and poly(2-ethyl-2-oxazoline); (g) 1,2,4-triazole, 1,2,3-triazole, benzotriazole and combinations thereof; and (f) combinations thereof.

4. The chemical mechanical planarization polishing composition according to any one of claims 1 to 3, wherein the concentration of the chemical additive is in the range of 0.01% to 20.0% by weight, 0.05% to 15% by weight, or 0.1% to 10% by weight.

5. The chemimechanical planarization polishing composition according to any one of claims 1 to 4, wherein the benzoic acid, its derivatives, or salts thereof have a general molecular structure selected from the following: (a) (b) and their combinations; in R1, R2, R3, R4, and R5 are each independently selected from hydrogen, hydroxyl, alkyl, alkoxy, amino, dialkylamino, alkylthio, and combinations thereof; and each of them may be attached to the -2, -3, -4, -5, or -6 position on the benzene ring; and M + It is a metal ion selected from potassium ions, ammonium ions, and sodium ions.

6. The chemimechanical planarization polishing composition according to any one of claims 1 to 5, wherein the biocide is selected from benzoic acid, potassium salt of benzoic acid, ammonium salt of benzoic acid, sodium salt of benzoic acid, potassium salt of benzoic acid, ammonium salt of sorbic acid, sodium salt of sorbic acid, potassium salt of sorbic acid, sorbitol, and combinations thereof.

7. The chemimechanical planarization polishing composition according to any one of claims 1 to 6, wherein the biocide is selected from potassium salts of benzoic acid, ammonium salts of benzoic acid, and combinations thereof.

8. The chemimechanical planarization polishing composition according to any one of claims 1 to 7, wherein the biocide is selected from benzoic acid, 2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 4-methoxybenzoic acid, 4-methylbenzoic acid, 2,6-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, etc. Methoxy-4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 4-(dimethylamino)benzoic acid, 3,5-diaminobenzoic acid, 2-methoxybenzoic acid, 2-ethoxybenzoic acid, 2-aminobenzoic acid, 3-methylthiobenzoic acid, 4-methylthiobenzoic acid, and combinations thereof.

9. The chemimechanical planarization polishing composition according to any one of claims 1 to 8, wherein the concentration of the biocide is in the range of 0.005% to 1.0% by weight, about 0.01% to 0.75% by weight, or about 0.05% to 0.5% by weight.

10. The chemical mechanical planar polishing composition according to any one of claims 1 to 9, wherein the chemical mechanical planar polishing composition comprises the abrasive selected from pyrolytic silica, colloidal silica, pyrolytic alumina, colloidal alumina, cerium oxide, titanium dioxide, zirconium oxide; inorganic oxide particles coated with metal oxides; organic polymer particles; organic polymer particles coated with metal oxides; and combinations thereof.

11. The chemical mechanical planar polishing composition according to claim 10, wherein the concentration of the abrasive is in the range of 0.01 wt% to 30 wt%, about 0.05 wt% to 20 wt%, about 0.01 to about 10 wt%, or about 0.1 wt% to 5 wt%.

12. The chemimechanical planar polishing composition according to any one of claims 1 to 11, wherein the chemimechanical planar polishing composition comprises the oxidant selected from peroxides and non-peroxides, and combinations thereof, wherein the peroxide is selected from hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, peroxypropionic acid, substituted or unsubstituted peroxybutyric acid, hydroperoxyacetaldehyde, potassium periodate, and ammonium persulfate; and the non-peroxide is selected from ferrous nitrite, KClO4, KBrO4, and KMnO4.

13. The chemical mechanical planarization polishing composition according to claim 12, wherein the concentration of the oxidant is in the range of about 0.01% by weight to 30% by weight, about 0.1% by weight to 20% by weight, or about 0.5% by weight to about 10% by weight.

14. The chemical mechanical planar polishing composition according to any one of claims 1 to 13, wherein the chemical mechanical planar polishing composition comprises an activator selected from the following: (1) inorganic oxide particles coated on the surface of a transition metal, wherein the transition metal is selected from Fe, Cu, Mn, Co, Ce and combinations thereof; (2) a soluble catalyst selected from ferric nitrate (III), ferric (III) ammonium oxalate trihydrate, ferric (III) citrate monohydrate, ferric acetylacetone (III), ethylenediaminetetraacetic acid, sodium iron (III) salt hydrate and combinations thereof; (3) a metal compound having a variety of oxidation states selected from Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V and combinations thereof; and combinations thereof.

15. The chemical mechanical planarization polishing composition according to claim 14, wherein the concentration of the activator ranges from about 0.00001 wt% to 5 wt%, from about 0.0001 wt% to 2.0 wt%, from about 0.0005 wt% to 1.0 wt%; or from about 0.001 wt% to 0.5 wt%.

16. A chemical mechanical planarization polishing method for chemical mechanical planarization of a semiconductor substrate, said semiconductor substrate comprising at least one surface containing at least one material, the method comprising the following steps: Make at least one surface contact the polishing pad; Deliver the chemical mechanical planarization polishing composition according to any one of claims 1 to 15; and Polish the at least one surface containing at least one material using the chemical mechanical planarization composition; The at least one material is selected from metals, metal alloys, new metals, barrier layer materials, dielectric materials, low-k and ultra-low-k materials, and combinations thereof.

17. The chemical mechanical planar polishing method according to claim 16, wherein the at least one material is selected from W, Cu, Co, Al, Ni, Mn, Ru, Ta, TaN, Ti, TiN, SiO2, SiN, SiC, black diamond, and combinations thereof.

18. A chemical mechanical planar polishing system, comprising: A semiconductor substrate, comprising at least one surface containing at least one material; Polishing pad; and The chemical mechanical planarization polishing composition according to any one of claims 1 to 15; The at least one surface containing at least one material is in contact with the polishing pad and the chemimechanical planarization composition; and The at least one material is selected from metals, metal alloys, new metals, barrier layer materials, dielectric materials, low-k and ultra-low-k materials, and combinations thereof.

19. The chemical mechanical planar polishing system according to claim 18, wherein the at least one material is selected from W, Cu, Co, Al, Ni, Mn, Ru, Ta, TaN, Ti, TiN, SiO2, SiN, SiC, black diamond, and combinations thereof.

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