WO2025111138A1 - Biocides pour compositions de polissage par planarisation chimico-mécanique (cmp) - Google Patents

Biocides pour compositions de polissage par planarisation chimico-mécanique (cmp) Download PDF

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WO2025111138A1
WO2025111138A1 PCT/US2024/054665 US2024054665W WO2025111138A1 WO 2025111138 A1 WO2025111138 A1 WO 2025111138A1 US 2024054665 W US2024054665 W US 2024054665W WO 2025111138 A1 WO2025111138 A1 WO 2025111138A1
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chemical mechanical
mechanical planarization
polishing composition
acid
group
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James Matthew Henry
Xiaobo Shi
Jeffery FERRENDELLI
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Versum Materials US LLC
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Versum Materials US LLC
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions

Definitions

  • CMP Chemical Mechanical Planarization
  • This invention relates to Chemical Mechanical Planarization (CMP) polishing compositions. More specifically, the invention relates to the protection of Chemical Mechanical Planarization (CMP) polishing compositions using biocides for inhibiting microbiological growth (bacteria and/or fungi) in the composition.
  • CMP Chemical Mechanical Planarization
  • US3,336,236 addressed the issue using sodium chlorite in an amount sufficient to inhibit growth and reproduction of the bacteria; US 3,816,330 addressed the issue using about 10-1000 parts per million of hexachlorophene; US 3,860,431 and US 2,823,186 addressed the issue using polyhydric alcohols; US2,801 ,216 and 3,046,234 addressed the issue using dialdehydes; US3,377,275 and 3,148,110 addressed the issue using formaldehyde; however, the aforementioned methods have unacceptable polishing rates.
  • US 4,169,337; US 4,462,188; US 4,588,421 ; and US 4,892,612 taught the use of various polishing rate accelerator to boost the polishing rates.
  • US 5,230,833 addressed the issue with the use of 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.
  • the preferred biocide is sodium chlorite or sodium hypochlorite; and the preferred fungicide is sodium OMADINE® (pyrithone).
  • W0200160940 indicated that the above chemicals used for inhibiting the microbiological growth are not always compatible with abrasive slurries used for chemical-mechanical polishing (CMP) of semiconductor wafers and with abrasive free slurries used with fixed abrasive polishing pads for semiconductor wafer polishing.
  • CMP chemical-mechanical polishing
  • WO200160940 disclosed the use of a five membered organic ring compound containing both a sulfur and a nitrogen in the ring which provides biocide protection of CMP slurries without affecting polishing performance.
  • CMIT 5-chloro-2- methyl-4-isothiazolin-3-one
  • MIT 2-methyl-4-isothiazolin-3-one
  • US 8,999,193 disclosed the use of MIP and CMIP as the biocides in tungsten CMP polishing composition
  • US10,600,655 disclosed the use of MIP and CMIP as the biocides in Shallow Trench Isolation (STI) CMP polishing composition
  • 11 ,718,767 disclosed the use of MIP and CMIP as the biocides in SiN CMP polishing composition.
  • heterocyclic organic compounds are known to be hazardous for the environment: wastewater treatment system, human health, highly toxic to the aquatic life, and worst, the long lasting effects.
  • EWG Environmental Working Group
  • the present invention satisfies the need by providing more friendly chemicals as alternative biocides in CMP polishing compositions.
  • the present invention discloses the use of chemicals that are much more environmentally friendly as the effective biocides in CMP polishing compositions.
  • ethylhexylglycerin has EWG score of 2; and caprylyl glyceryl ether, and caprylyl glyceryl ether has EWG score of 1 .
  • Those chemicals are much more environmental-friendly than the commonly used biocides containing MIT, OMIT and OIT in CMP polishing compositions.
  • a CMP polishing composition comprising, consisting essentially of, or consisting of: a chemical additive; a biocide; and water-soluble solvent; and optionally at least one of abrasive; a pH adjusting agent; an oxidizer; an activator; a surfactant; and a corrosion inhibitor; wherein the biocide comprises an organic compound with at least one diol functional group at one end of the organic compound and with at least one organic alkyl ether group at the other end of the organic compound; wherein the organic alkyl ether group has at least one straight or branched alkyl chain connecting to the oxygen atom in the organic alkyl ether group; pH of the polishing composition ranges from 2 to 9, 2 to 8, 2 to 7, or 2 to 6.
  • the chemical additive can be any additives that promote microbiological growth in a CMP polishing composition
  • the chemical additive includes but is not limited to any chemicals that perform a function in a CMP polishing composition as a dishing reducer, a removal rate suppressor, a removal rate accelerator, a surfactant, a corrosion inhibitor, an erosion reducer, defect reducer, dispersion agent, chelating agent, stabilizer, and combinations thereof in a CMP polishing composition.
  • Those functions have their commonly acceptable meanings in the art and should be readily understood by a person of ordinary skill in the art. For instance, a dishing reducer reduces the dishing during polishing; an organic rate accelerator/suppressor enhances/suppresses polishing rate of a material to be polished.
  • the biocide includes but is not limited to an organic compound having a general molecular structure of: and combinations thereof; where each of Ri, R2 , and R 3 is independently an organic alkyl group with -(CH 2 ) n -CH 3 moieties with n ranging from 1 to 12.
  • the optional abrasive includes but is not limited to inorganic oxide particles, metal oxide-coated inorganic oxide particles, organic polymer particles, metal oxidecoated organic polymer particles, and combinations thereof.
  • the optional pH adjusting agent includes but is 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 to lower the pH; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and mixtures thereof to raise the pH.
  • the optional oxidizer includes but is not limited to peroxy compound selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, propaneperoxoic acid, substituted or unsubstituted butaneperoxoic acid, hydroperoxy-acetaldehyde, potassium periodate, and ammonium peroxymonosulfate; and non-per-oxy compound selected from the group consisting of ferric nitrite, KCIO4, KBrO4, and KMnO4; and combinations thereof.
  • peroxy compound selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, propaneperoxoic acid, substituted or unsubstituted butaneperoxoic acid, hydroperoxy-acetaldehyde, potassium periodate, and ammonium peroxymonosulfate
  • non-per-oxy compound selected from the group consisting of ferric nitrite, KCIO4, KBr
  • the optional activator includes but is not limited to (1 ) inorganic oxide particle with transition metal coated onto its surface; wherein the transition metal is selected from the group consisting of Fe, Cu, Mn, Co, Ce, and combinations thereof; (2)soluble catalyst selected from the group consisting of iron (III) nitrate, ammonium iron (III) oxalate trihydrate, iron(lll) citrate tribasic monohydrate, iron(lll) acetylacetonate, ethylenediamine tetraacetic acid, iron (III) sodium salt hydrate, and combinations thereof; (3) a metal compound having multiple oxidation states selected from the group consisting of Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V, and combinations thereof; and combinations thereof.
  • the optional surfactant can be any surfactant which includes but is not limited to non-ionic surfactant, anionic surfactant, cationic surfactant, ampholytic surfactant, and mixtures thereof.
  • the optional corrosion inhibitor can be any corrosion inhibitor which includes but is not limited to nitrogenous cyclic compounds.
  • a CMP polishing method for chemical mechanical planarization of a semiconductor substrate comprising at least one surface containing at least one material, comprising the steps of: contacting the at least one surface with a polishing pad; delivering the CMP polishing composition of Aspect 1 ; polishing the at least one surface containing the at least one material with the CMP polishing composition.
  • a CMP polishing system comprising: a semiconductor substrate comprising at least one surface containing at least one material; a polishing pad; and the CMP polishing composition of Aspect 1 ; wherein the at least one surface containing the at least one material is in contact with the polishing pad and the CMP polishing composition.
  • the at least one material refers to any materials used in the semiconductor substrate or patten wafer; includes metals or metal alloys such as W, Cu, Co, Al, Ni, Mn, and their alloys; novel 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.
  • metals or metal alloys such as W, Cu, Co, Al, Ni, Mn, and their alloys
  • novel metals such as Ru
  • barrier layer materials such as Ta, TaN, Ti, TiN, and Co
  • dielectric materials such as SiO2, SiN, and SiC
  • low-k and ultra-low-k materials such as Black Diamond.
  • the present invention satisfies the need by providing desirable friendly chemicals as alternative biocides in CMP polishing compositions; as well as in the systems, and methods of using the CMP polishing composition or slurry.
  • composition and slurry are exchangeable.
  • the invention discloses the biocides which prohibit microbiological growth in a CMP polishing composition that contains chemical additives promoting microbiological growth.
  • the CMP polishing composition can be abrasive free CMP polishing compositions which is used with fixed abrasive polishing pads for semiconductor wafer polishing.
  • the CMP polishing composition can also contain more than one part, such as two parts: the chemical package and the abrasive package wherein the two packages will be mixed together at the point of use.
  • the chemical package usually contains the chemical additives that promote microbiological growth, and thus the chemical package usually contains the biocide.
  • the packages can also be concentrated and will be diluted at the point of use.
  • a CMP polishing composition comprising, consisting essentially of, or consisting of: a chemical additive; a biocide; and water-soluble solvent; and optionally at least one of abrasive; a pH adjusting agent; an oxidizer; an activator; a surfactant; and a corrosion inhibitor; wherein the biocide comprises an organic compound with at least one diol functional group at one end of the organic compound and with at least one organic alkyl ether group at the other end of the organic compound; wherein the organic alkyl ether group has at least one straight or branched alkyl chain connecting to the oxygen atom in the organic alkyl ether group; pH of the composition ranges from 2 to 9, 2 to 8, 2 to 7, or 2 to 6.
  • the chemical additive can be any additive that promote microbiological growth.
  • the chemical additive includes but is not limited to any chemicals that perform a function in a CMP polishing composition as a dishing reducer, a removal rate suppressor, a removal rate accelerator, a surfactant, a corrosion inhibitor, an erosion reducer, defect reducer, dispersion agent, chelating agent, stabilizer, and combinations thereof in a CMP polishing composition.
  • Those functions have their commonly acceptable meanings in the art and should be readily understood by a person of ordinary skill in the art. For instance, a dishing reducer reduces the dishing during polishing; an organic rate accelerator/suppressor enhances/suppresses polishing rate of a material to be polished.
  • the chemical additive can be a dishing reducer such as (a) a polyol includes but is not limited to maltitol, lactitol, maltotritol, ribitol, D-sorbitol, mannitol, dulcitol, iditol, D-(-)-Fructose, sorbitan, sucrose, ribose, Inositol, glucose, D-arabinose, L-arabinose, D-mannose, L-mannose, meso-erythritol, beta-lactose, arabinose, fructose, xylitol, and combinations thereof, as disclosed in US11 ,078,417 for STI polishing composition; (b)1 ,8-Diazabicyclo(5.4.0)undec-7-ene(DBU), and/or 2- aminobenzoimidazole for W polishing composition as disclosed in US20200040256; and (c)1 ,
  • the chemical additive can also be a removal rate accelerator such as (a) organic sulfonic acid, organic aromatic sulfonic acid such as benzene sulfonic acid, piperazine, organic phosphonic acid, for STI polishing composition as disclosed in US2020004,551 ; (b)organic carboxylic acids for W polishing composition as disclosed in US20200040256; and (c)various amino acids such as glycine and alanine, amino acid derivatives, and organic amines for Cu polishing composition as disclosed in US9,978,609.
  • a removal rate accelerator such as (a) organic sulfonic acid, organic aromatic sulfonic acid such as benzene sulfonic acid, piperazine, organic phosphonic acid, for STI polishing composition as disclosed in US2020004,551 ; (b)organic carboxylic acids for W polishing composition as disclosed in US20200040256; and (c)various amino acids such as glycine and alanine, amino acid derivatives,
  • the chemical additive can also be a polymer or co-polymer includes but is not limited to polyacrylic acid, polymethylcrylic acid, polyamide, polystyrene sulfonic acid, polyamine, polyethyleneimine, polyethylene oxide, polypropylene oxide, polyethylene glycol, polyglycerin, polyoxyethylene, polyglyceryl ether, polyoxypropylene, polyglyceryl ether, polyacrylamide, poly(acrylic acid-co-maleic acid), poly(acrylamide-co-acrylic acid), poly(methyl vinyl ether), polypropylene glycol), poly(2-acrylamido-2-methyl-1 - propanesulfonic acid), poly(1 -vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate), polyvinyl sulfonic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl pyrdine-N-oxide, Poly(acrylamide-acrylic acid), poly(4
  • the concentration (or amount) of chemical additive ranges from 0.01 wt.% to 20.0 wt.%, 0.05 wt.% to 15 wt.%, or 0.1 wt.% to 10 wt.%.
  • the weight percent is relative to the composition.
  • the biocide includes but is not limited to an organic compound with at least one diol functional group at one end of the organic compound and with at least one organic alkyl ether group at the other end of the organic compound; wherein the organic alkyl ether group has at least one straight or branched alkyl chain connecting to the oxygen atom in the organic alkyl ether group;
  • the biocide can have a general molecular structure including but not being limited to: and combinations thereof; wherein each of R1 , R2 and R3 is independently an organic alkyl group with - (CH 2 )n-CH 3 moieties having n ranging from 1 to 12.
  • R1 , R2 and R3 is independently an organic alkyl group with - (CH 2 )n-CH 3 moieties having n ranging from 1 to 12.
  • Specific examples are ethylhexylglyceirn which has the general molecular structure (b) having R2 as ethyl group and R3 as butyl group; heptylglyceryl ether and caprylyl glyceryl ether which have the general molecular structure (a) having R1 as hexyl group and heptyl group respectively: caprylyl glyceryl ether.
  • Ethylhexylglycerin, heptylglyceryl ether and caprylyl glyceryl ether are widely used in skincare products which are more friendly for human skin.
  • they are the main ingredients for SaksineTM 50 (main ingredient: ethylhexylglycerin), SaksineTM 70 ( main ingredient: heptylglyceryl ether), and SaksineTM 80 (main ingredient: caprylyl glyceryl ether) of SaskineTM products from SACHEM, Inc..
  • the concentration of the biocide can range from about 0.005 wt.% to 2.0 wt.%, about 0.01 wt.% to 1 .5 wt.%, 0.05 to 1 .0 wt.%; or 0.075 to 0.5 wt.%.
  • the weight percent is relative to the composition.
  • the water-soluble solvent includes but is not limited to deionized (DI) water, distilled water, and alcoholic organic solvents.
  • the optional abrasive includes but is not limited to inorganic oxide particles including but not being limited to fumed silica, colloidal silica, high purity colloidal silica, fumed alumina, colloidal alumina, cerium oxide, titanium dioxide, zirconium oxide; metal oxide-coated inorganic oxide particles including but not being limited to ceria-coated inorganic oxide particles; organic polymer particles; metal oxide-coated organic polymer particles; and combinations thereof.
  • the concentration of the abrasive can range from about 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.%.
  • the weight percent is relative to the composition.
  • the abrasive particles have mean particle sizes (measured by Dynamic Light Scattering DLS technology) ranging from about 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.
  • the optional oxidizer includes but is not limited to peroxy compound selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, propaneperoxoic acid, substituted or unsubstituted butaneperoxoic acid, hydroperoxy-acetaldehyde, potassium periodate, and ammonium peroxymonosulfate, and non-per-oxy compound selected from the group consisting of ferric nitrite, KCIO4, KBrO 4 , and KMnC ; and combinations thereof.
  • the oxidizer concentration can range from about 0.01 wt.% to 30 wt.%, about 0.1 wt.% to 20 wt.%, or about 0.5 wt.% to about 10 wt.%.
  • the weight percent is relative to the composition.
  • the optional activator includes but is not limited to (1 ) inorganic oxide particle with transition metal coated onto its surface; wherein the transition metal is selected from the group consisting of Fe, Cu, Mn, Go, Ce, and combinations thereof; (2)soluble catalyst selected from the group consisting of iron (III) nitrate, ammonium iron (III) oxalate trihydrate, iron(lll) citrate tribasic monohydrate, iron(lll) acetylacetonate, ethylenediamine tetraacetic acid, iron (III) sodium salt hydrate, and combinations thereof; (3) a metal compound having multiple oxidation states selected from the group consisting of Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V, and combinations thereof; and combinations thereof.
  • the amount of the activator can range from 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.%.
  • the optional surfactant can be any surfactant includes but is not limited to non-ionic surfactant, anionic surfactant, cationic surfactant, ampholytic surfactant, and mixtures thereof.
  • Non-ionic surfactants may be chosen from a range of chemical types including but not limited to long chain alcohols, ethoxylated alcohols, ethoxylated acetylenic diol surfactants, polyethylene glycol alkyl ethers, proplylene glycol alkyl ethers, glucoside alkyl ethers, polyethylene glycol octylphenyl ethers, polyethylene glycol alkylpgenyl ethers, glycerol alkyl esters, polyoxyethylene glycol sorbiton alkyl esters, sorbiton alkyl esters, cocamide monoethanol amine, cocamide diethanol amine dodecyl dimethylamine oxide, block copolymers of polyethylene glycol and polypropylene
  • Anionic surfactants include, but are not limited to salts with suitable hydrophobic tails, such as alkyl carboxylate, alkyl polyacrylic salt, alkyl sulfate, alkyl phosphate, alkyl bicarboxylate, alkyl bisulfate, alkyl biphosphate, such as alkoxy carboxylate, alkoxy sulfate, alkoxy phosphate, alkoxy bicarboxylate, alkoxy bisulfate, alkoxy biphosphate, such as substituted aryl carboxylate, substituted aryl sulfate, substituted aryl phosphate, substituted aryl bicarboxylate, substituted aryl bisulfate, and substituted aryl biphosphate etc.
  • the counter ions for this type of surfactants include, but are not limited to potassium, ammonium and other positive ions.
  • the molecular weights of these anionic surface wetting agents range from several hundred to several hundredthousand.
  • Cationic surfactants possess the positive net charge on major part of molecular frame.
  • Cationic surfactants are typically halides of molecules comprising hydrophobic chain and cationic charge centers such as amines, quaternary ammonium, benzyalkonium, and alkylpyridinium ions.
  • the surfactant can be an ampholytic surfactant, which possess both positive (cationic) and negative (anionic) charges on the main molecular chains and with their relative counter ions.
  • the cationic part is based on primary, secondary, or tertiary amines or quaternary ammonium cations.
  • the anionic part can be more variable and include sulfonates, as in the sultaines CHAPS (3-[(3- Cholamidopropyl)dimethylammonio]-1 -propanesulfonate) and cocam idopropyl hydroxysultaine. Betaines such as cocamidopropyl betaine have a carboxylate with the ammonium.
  • ampholytic surfactants may have a phosphate anion with an amine or ammonium, such as the phospholipids phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelins.
  • the amount of the surfactant can range from 0.0001 wt.% to 10 wt.%, 0.01 wt.% and 3 wt.%, or 0.05 wt.% and 1 wt.%.
  • the optional corrosion inhibitor can be any corrosion inhibitor, includes but is not limited to nitrogenous 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 amino triazole, benzimidazole, benzothiazoles such as 2,1 ,3-benzothiadiazole, triazinethiol, triazinedithiol, and triazinetrithiol, pyrazoles, imidazoles, isocyanurate such as 1 ,3,5- tris(2-hydroxyethyl), and mixtures thereof.
  • Preferred inhibitors are 1 ,2,4-triazole, 5 amino triazole and 1 ,3,5-tris(2-hydroxyethy
  • the amount of the corrosion inhibitor can range from less than 1 .0 wt.%, less than 0.5 wt.%, or less than 0.25 wt.%.
  • a CMP polishing method for chemical mechanical planarization of a semiconductor substrate comprising at least one surface containing at least one material, comprising the steps of: contacting the at least one surface with a polishing pad; delivering the CMP polishing composition of Aspect 1 ; polishing the at least one surface containing the at least one material with the CMP polishing composition.
  • a CMP polishing system comprising: a semiconductor substrate comprising at least one surface containing at least one material; a polishing pad; and the CMP polishing composition of Aspect 1 ; wherein the at least one surface containing the at least one material is in contact with the polishing pad and the CMP polishing composition.
  • the at least one material refers to any materials used in the semiconductor substrate or patten wafer; includes metals or metal alloys such as W, Cu, Co, Al, Ni, Mn, and their alloys; novel metals such as Ru; barrier layer materials such as Ta, TaN, Ti, TiN, Co, and combinations thereof; dielectric materials such as SiO2, SiN, SiC, and combinations thereof; and low-k and ultra-low-k materials, such as Black Diamond.
  • metals or metal alloys such as W, Cu, Co, Al, Ni, Mn, and their alloys
  • novel metals such as Ru
  • barrier layer materials such as Ta, TaN, Ti, TiN, Co, and combinations thereof
  • dielectric materials such as SiO2, SiN, SiC, and combinations thereof
  • low-k and ultra-low-k materials such as Black Diamond.
  • Ceria-coated Silica used as abrasive having a particle size of approximately 20 nanometers (nm) to 500 nanometers (nm);
  • Ceria-coated Silica particles (with varied sizes) were supplied by JGCC Inc. in Japan.
  • Chemicals such as D-Sorbitol, and other chemical raw materials were supplied by MilliporeSigma, St. Louis, MO. Chemicals SaskineTM 50, SaskineTM 70, and SaskineTM 80 were supplied by Sachem Inc located in Austin, Texas.
  • Biocide Efficacy Testing was performed with the intentional additions of microbe (bacteria and fungi). All tests were done at a temperature of 30°C.
  • the first reference (Ref. 1 ) contained 15 wt.% D-sorbitol, pH adjusting agent, deionized water and no biocide with pH being adjusted to 2.15.
  • the working samples #1 , #2 and #3 added 0.1 wt.% SaskineTM 50, SaskineTM 70, and SaskineTM 80 as the alternative biocide in Ref. 1 respectively.
  • the pH was adjusted to about 2.1 .
  • the second reference (Ref. 2) contained 15 wt.% D-sorbitol, pH adjusting agent, deionized water and no biocide with pH being adjusted to 7.0.
  • the working samples #4, #5, and # 6 used 15 wt.% D-Sorbitol, 0.1 wt.% SaskineTM 50, SaskineTM 70, and SaskineTM 80 respectively as the alternative biocide, and deionized water with pH being adjusted to 7.0.
  • the working samples contained 15 wt.% D-sorbitol, pH adjusting agent, deionized water, and different concentrations of alternative biocides SaskineTM 70 and SaskineTM 80 : working samples #7, #8 and #9 having 0.01 wt. %, 0.05 wt. % and 0.1 wt. % of SaskineTM 70 respectively; and working samples #10, #11 and #12 having 0.01 wt. %, 0.05 wt. % and 0.1 wt. % of SaskineTM 80, respectively.
  • Reference 3 (Ref. 3) was composed of 17.5 wt.% calcined ceria particles, 0.875 wt.% polyacrylic acid, pH adjusting agent and deionized water. No biocide was used.
  • the working polishing composition #13 was composed of the 17.5 wt.% calcined ceria particles and 0.875 wt.% polyacrylic acid, pH adjusting agent, deionized water and 0.1 wt.% SaskineTM 50 (ethylhexylglycerin).
  • the working polishing composition #14 was composed of the 17.5 wt.% calcined ceria particles and 0.875 wt.% polyacrylic acid, pH adjusting agent, deionized water and 0.1 wt.% SaskineTM 80 (caprylyl glyceryl ether).
  • biocide efficacy test results proved that more friendly type of biocides can be used in the pH range of 2 to 7 in the CMP polishing compositions as the effective biocide and can be used directly to replace the commonly used MIT, CMIT or OIT type of biocide in CMP polishing compositions.
  • a or A angstrom(s) - a unit of length
  • BP back pressure, in psi units
  • DF Down force: pressure applied during CMP, unit: psi
  • PS platen rotational speed of polishing tool, in rpm (revolution(s) per minute)
  • TEOS SiN Selectivity: (removal rate of TEOS)/ (removal rate of SiN)
  • HDP high density plasma deposited TEOS
  • TEOS or HDP Removal Rates Measured TEOS or HDP removal rate at a given down pressure.
  • the down pressure of the CMP tool was 2.0, 3.0 or 4.0 psi in the examples.
  • SiN Removal Rates Measured SiN removal rate at a given down pressure.
  • the down pressure of the CMP tool was 3.0 psi in the examples listed.
  • ResMap CDE model 168, manufactured by Creative Design Engineering, Inc, 20565 Alves Dr., Cupertino, CA, 95014.
  • the ResMap tool is a four-point probe sheet resistance tool. Forty-nine-point diameter scan at 5mm edge exclusion for film was taken.
  • the CMP tool that was used is a 200mm Mirra, or 300mm Reflexion manufactured by Applied Materials, 3050 Boweres Avenue, Santa Clara, California, 95054.
  • An IC1010 pad supplied by DOW, Inc, 451 Bellevue Rd., Newark, DE 19713 was used on platen 1 for blanket and pattern wafer studies.
  • the IC1010 pad or other pad was broken in by conditioning the pad for 18 mins. At 7 lbs. down force on the conditioner. To qualify the tool settings and the pad break-in four TEOS monitors were polished with Versum® STI2305 composition, supplied by Versum Materials Inc. at baseline conditions.
  • Polishing experiments were conducted using PECVD or LECVD or HD TEOS wafers, and SiN wafers, the patterned wafer are MIT864 oxide patterned wafer. These blanket and patterned wafers were purchased from Silicon Valley Microelectronics, 2985 Kifer Rd., Santa Clara, CA 95051 . [00110] In blanket wafer studies, oxide blanket wafers, and SiN blanket wafers were polished at baseline conditions. The tool baseline conditions were: table speed; 87 rpm, head speed: 93 rpm, membrane pressure; 3.1 psi, composition flow; 200 ml/min., Saesol E4 disk was used for 100% in-situ conditioning.
  • the reference polishing composition number one (Ref. 1 ) contained 0.5 wt.% ceria-coated silica abrasive, 0.15 wt.% D-sorbitol 18.6 ppm bioban 425 (2-octyl-2H- isothiazole-3-one, OIT biocide) as biocide, pH adjusting agent, and deionized water. The pH was adjusted to 5.35.
  • the reference polishing composition number two (Ref. 2) contained 0.5 wt.% ceria-coated silica abrasive, 0.15 wt.% D-sorbitol, pH adjusting agent, and deionized water. The pH was adjusted to 5.35.
  • the working polishing composition 1 (Sample# 1) contained 0.5 wt.% ceria- coated silica abrasive, 0.15 wt.% D-sorbitol, 25.0 ppm SaskineTM 50 (ethylhexylglycerin) as eco-friendly biocide, pH adjusting agent, and deionized water. The pH was adjusted to 5.35.
  • the working polishing composition 2(Sample# 2) contained 0.5 wt.% ceria- coated silica abrasive, 0.15 wt.% D-sorbitol, 50.0 ppm SaskineTM 50 (ethylhexylglycerin) as eco-friendly biocide, pH adjusting agent, and deionized water. The pH was adjusted to 5.35.
  • SiN trench loss rates from patterned wafer polishing were obtained from two reference samples and the working samples on different size features. The results were listed in Table 8.
  • CMP polishing example 6 another set of removal rates of different films, oxide trench pitch dishing on different size features vs different over polishing times and oxide trench dishing rates on different size features were measured. RR Selectivity were also calculated.
  • the reference polishing composition number 3 (Ref. 3) contained 0.5 wt.% calcined ceria abrasive, and 0.05 wt.% polyacrylic acid, 7.5ppm neoIone M10 (methyl isothiazolinone MIT based biocide) as biocide, pH adjusting agent, and deionized water. The pH was adjusted to 5.35.
  • the reference polishing composition number 4 (Ref. 4) contained 0.5 wt.% calcined ceria abrasive, 0.05 wt.% polyacrylic acid, and no biocide, pH adjusting agent, and deionized water. The pH was adjusted to 5.35.
  • the working polishing composition 3 contained 0.5 wt.% calcined ceria abrasive, 0.05 wt.% polyacrylic acid, 7.15ppm SaskineTM 50 (ethylhexylglycerin) as eco-friendly biocide, pH adjusting agent, and deionized water. The pH was adjusted to 5.35.
  • the working polishing composition 4 (Sample# 4) contained 0.5 wt.% calcined ceria abrasive, 0.05 wt.% polyacrylic acid, 14.3ppm SaskineTM 50 (ethylhexylglycerin) as eco-friendly biocide, pH adjusting agent, and deionized water. The pH was adjusted to 5.35.
  • the working polishing composition 5 contained 0.5 wt.% calcined ceria abrasive, 0.05 wt.% polyacrylic acid, 21 ,4ppm SaskineTM 50 (ethylhexylglycerin) as eco-friendly biocide, pH adjusting agent, and deionized water. The pH was adjusted to 5.35.
  • the working polishing composition 6(Sample# 6) contained 0.5 wt.% calcined ceria abrasive, 0.05 wt.% polyacrylic acid, and 28.6ppm SaskineTM 50 (ethylhexylglycerin) as eco-friendly biocide, pH adjusting agent, and deionized water. The pH was adjusted to 5.35.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

La présente invention concerne des biocides pour inhiber la croissance de microbes (bactéries et/ou champignons) dans des compositions de polissage par planarisation chimico-mécanique (CMP). Le biocide comprend des composés organiques ayant au moins un groupe fonctionnel diol à une extrémité du composé, et au moins un groupe éther alkylique organique à l'autre extrémité du composé.
PCT/US2024/054665 2023-11-22 2024-11-06 Biocides pour compositions de polissage par planarisation chimico-mécanique (cmp) Pending WO2025111138A1 (fr)

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US3046234A (en) 1959-12-07 1962-07-24 Monsanto Chemicals Stable alkaline silica sols containing certain dialdehydes
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US10600655B2 (en) 2017-08-10 2020-03-24 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Chemical mechanical polishing method for tungsten
CN111423819A (zh) * 2020-04-17 2020-07-17 深圳市朗纳研磨材料有限公司 抛光液及其制备方法
US11078417B2 (en) 2018-06-29 2021-08-03 Versum Materials Us, Llc Low oxide trench dishing chemical mechanical polishing
US11401441B2 (en) 2017-08-17 2022-08-02 Versum Materials Us, Llc Chemical mechanical planarization (CMP) composition and methods therefore for copper and through silica via (TSV) applications
US20230287243A1 (en) * 2022-03-08 2023-09-14 Fujimi Incorporated Polishing composition, polishing method, and method of manufacturing semiconductor substrate

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2823186A (en) 1955-09-14 1958-02-11 Monsanto Chemicals Silica aquasol containing a polyhydric alcohol
US2801216A (en) 1956-04-05 1957-07-30 Union Carbide & Carbon Corp Treatment of water with dialdehyde bactericides
US3046234A (en) 1959-12-07 1962-07-24 Monsanto Chemicals Stable alkaline silica sols containing certain dialdehydes
US3148110A (en) 1962-11-07 1964-09-08 Du Pont Method of disinfecting with formaldehyde-colloidal silica aquasols
US3336236A (en) 1964-12-23 1967-08-15 Nalco Chemical Co Aqueous colloidal sio sols stabilized against bacterial contamination
US3377275A (en) 1965-06-17 1968-04-09 Nalco Chemical Co Treatment for aqueous industrial process fluids
US3816330A (en) 1970-10-05 1974-06-11 Du Pont Method of protecting colloidal silica aquasols from bacterial degradation
US3860431A (en) 1972-04-28 1975-01-14 Nalco Chemical Co Slip resistant composition for paper coating
US4169337A (en) 1978-03-30 1979-10-02 Nalco Chemical Company Process for polishing semi-conductor materials
US4462188A (en) 1982-06-21 1984-07-31 Nalco Chemical Company Silica sol compositions for polishing silicon wafers
US4588421A (en) 1984-10-15 1986-05-13 Nalco Chemical Company Aqueous silica compositions for polishing silicon wafers
US4892612A (en) 1988-10-11 1990-01-09 Huff John E Polishing method
US5230833A (en) 1989-06-09 1993-07-27 Nalco Chemical Company Low sodium, low metals silica polishing slurries
JP2001085374A (ja) * 1999-07-13 2001-03-30 Kao Corp 研磨液組成物
WO2001060940A1 (fr) 2000-02-16 2001-08-23 Rodel Inc Biocides pour pates de polissage
US8999193B2 (en) 2012-05-10 2015-04-07 Air Products And Chemicals, Inc. Chemical mechanical polishing composition having chemical additives and methods for using same
US9978609B2 (en) 2015-04-27 2018-05-22 Versum Materials Us, Llc Low dishing copper chemical mechanical planarization
US10600655B2 (en) 2017-08-10 2020-03-24 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Chemical mechanical polishing method for tungsten
US11401441B2 (en) 2017-08-17 2022-08-02 Versum Materials Us, Llc Chemical mechanical planarization (CMP) composition and methods therefore for copper and through silica via (TSV) applications
JP2019104797A (ja) * 2017-12-11 2019-06-27 花王株式会社 研磨液組成物
US11078417B2 (en) 2018-06-29 2021-08-03 Versum Materials Us, Llc Low oxide trench dishing chemical mechanical polishing
US20200004551A1 (en) 2018-07-02 2020-01-02 Arm Limited Appratus and method for using predicted result values
US20200040256A1 (en) 2018-07-31 2020-02-06 Versum Materials Us, Llc Tungsten Chemical Mechanical Planarization (CMP) With Low Dishing And Low Erosion Topography
CN111423819A (zh) * 2020-04-17 2020-07-17 深圳市朗纳研磨材料有限公司 抛光液及其制备方法
US20230287243A1 (en) * 2022-03-08 2023-09-14 Fujimi Incorporated Polishing composition, polishing method, and method of manufacturing semiconductor substrate

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