Surface treatment composition and surface treatment method

Abstract

To provide a method and compositions for treating patterned wafers distributed on the surface of a wafer.SOLUTION: A method for treating a semiconductor substrate with a pattern arranged on the surface of a wafer, includes bringing the surface into contact with the composition for surface treatment to form a surface treatment layer such that the water contact angle of the surface treatment layer is about 50 degrees or more. The composition for surface treatment comprises at least one siloxane compound and at least one trialkylsilyl compound selected from the group consisting of trialkylsilyl alkyl sulfonates, trialkylsilyl arylsulfonates and trialkylsilyl acetates, and the pattern on the wafer surface contains features with dimensions of about 20 nm or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates generally to surface treatment, and more particularly to liquid treatment of semiconductor surfaces where the formation of a hydrophobic layer is desired. [Background technology]

[0002] In semiconductor manufacturing processes, pattern collapse of FinFETs and dielectric stacks during wet cleaning and drying is a major problem at critical dimensions such as sub-20 nm.The conventional theory of pattern collapse is that high capillary forces during cleaning and drying are the main contributor to the collapse phenomenon.

[0003] However, other chemical and substrate properties may also play an important role, such as the surface tension and viscosity of the liquid, the mechanical strength of the substrate, the density and aspect ratio of the patterns, and even damage to the substrate surface by the cleaning chemicals. Summary of the Invention

[0004] It has been discovered that low-surface tension modifying fluids that impart a hydrophobic layer (e.g., a hydrophobic monolayer) to the surface of a semiconductor substrate (e.g., a silicon or copper wafer) can minimize the capillary forces that cause pattern collapse during drying. Without intending to be bound by theory, it is believed that Laplace pressure is minimized when the contact angle, i.e., the angle that a liquid (e.g., water) forms when in contact with the substrate surface, is at or near 90 degrees. This, in combination with the presence of a low-surface tension fluid, can significantly reduce the forces that cause pattern collapse.

[0005] Generally, the present disclosure provides methods and compositions for treating a patterned surface of a semiconductor substrate (e.g., a patterned wafer) to form a hydrophobic layer on the surface, thereby minimizing or preventing pattern collapse when the surface undergoes typical cleaning and drying steps in a semiconductor manufacturing process. The methods disclosed herein use compositions that form a hydrophobic layer on the surface such that the water contact angle of the treated surface is about 50 degrees or greater.

[0006] In one aspect, the present disclosure provides a method for treating a semiconductor substrate having a pattern disposed on the surface of the wafer. The method includes contacting the surface with a surface treatment composition to form a surface treatment layer such that the surface treatment layer has a water contact angle of about 50 degrees or greater. The surface treatment composition can include (e.g., include, consist of, or consist essentially of) at least one solvent (e.g., at least one organic solvent) and at least one trialkylsilyl compound selected from the group consisting of trialkylsilyl alkyl sulfonates, trialkylsilyl aryl sulfonates, and trialkylsilyl acetates. The surface treatment composition can be substantially free of propylene glycol methyl ether acetate and can be substantially free of additional Si-containing compounds (e.g., siloxanes such as disiloxanes, silanes, silazanes) other than the at least one trialkylsilyl compound. The pattern can have features with dimensions of about 20 nm or less.

[0007] In yet another aspect, the present disclosure provides a surface treatment composition comprising (e.g., comprising, consisting of, or consisting essentially of) (1) about 0.1% to about 15% by weight of the surface treatment composition of at least one trialkylsilyl compound, the at least one trialkylsilyl compound being selected from the group consisting of trialkylsilyl alkyl sulfonates, trialkylsilyl aryl sulfonates, and trialkylsilyl acetates, and (2) about 1% to about 99% by weight of the surface treatment composition of at least one solvent (e.g., at least one organic solvent). The surface treatment composition may be substantially free of propylene glycol methyl ether acetate and may also be substantially free of additional Si-containing compounds (e.g., siloxanes such as disiloxanes, silanes, silazanes) other than the at least one trialkylsilyl compound.

[0008] In another aspect, the present disclosure provides a method for treating a semiconductor substrate having a pattern disposed on the surface of the wafer. The method includes contacting the surface with a surface treatment composition to form a surface treatment layer such that the water contact angle of the surface treatment layer is about 50 degrees or greater. The surface treatment composition can include (e.g., include, consist of, or consist essentially of) at least one siloxane compound and at least one trialkylsilyl compound selected from the group consisting of trialkylsilyl alkyl sulfonates, trialkylsilyl aryl sulfonates, and trialkylsilyl acetates. The pattern can have features with dimensions of about 20 nm or less.

[0009] In yet another aspect, the present disclosure provides a surface treatment composition comprising (e.g., comprising, consisting of, or consisting essentially of) (1) from about 0.1% to about 15% by weight of the surface treatment composition of at least one trialkylsilyl compound, the at least one trialkylsilyl compound being selected from the group consisting of trialkylsilyl alkyl sulfonates, trialkylsilyl aryl sulfonates, and trialkylsilyl acetates; and (2) from about 85% to about 99.9% by weight of the surface treatment composition of at least one siloxane compound.

[0010] In another aspect, the present disclosure provides a method for treating a semiconductor substrate having a pattern disposed on the surface of the wafer. The method can include contacting the surface with a surface treatment composition to form a surface treatment layer such that the water contact angle of the surface treatment layer is about 50 degrees or greater. The surface treatment composition can include (e.g., include, consist of, or consist essentially of) at least one solvent, at least one sulfonic acid or a salt thereof, and at least one trialkylsilyl compound selected from the group consisting of trialkylsilyl alkylsulfonates, trialkylsilyl arylsulfonates, and trialkylsilyl acetates. The surface treatment composition can be substantially free of additional Si-containing compounds other than the at least one trialkylsilyl compound. The pattern can have features with dimensions of about 20 nm or less.

[0011] In yet another aspect, the present disclosure provides a surface treatment composition comprising (e.g., comprising, consisting of, or consisting essentially of) (1) at least one sulfonic acid or salt thereof in an amount of about 0.01% to about 10% by weight of the surface treatment composition, (2) at least one trialkylsilyl compound selected from the group consisting of trialkylsilyl alkylsulfonates, trialkylsilyl arylsulfonates, and trialkylsilyl acetates in an amount of about 0.1% to about 15% by weight of the surface treatment composition, and (3) at least one solvent in an amount of about 1% to about 99% by weight of the surface treatment composition. The surface treatment composition may be substantially free of additional Si-containing compounds other than the at least one trialkylsilyl compound.

[0012] In yet another aspect, the present disclosure is directed to articles comprising a semiconductor substrate and a surface treatment composition according to the present disclosure supported on the semiconductor substrate.

[0013] Other features, objects, and advantages of the invention will become apparent from the description and claims. DETAILED DESCRIPTION OF THE INVENTION

[0014] In some embodiments, the present disclosure relates to a surface treatment method. Such a method can be carried out, for example, by contacting a surface (e.g., a patterned surface) of a substrate (e.g., a semiconductor substrate such as a silicon wafer or a copper wafer) with a surface treatment composition comprising at least one (e.g., two, three, or four) solvent and at least one (e.g., two, three, or four) trialkylsilyl compound selected from the group consisting of trialkylsilyl alkylsulfonates, trialkylsilyl arylsulfonates, and trialkylsilyl acetates. The pattern can have features with dimensions of about 20 nm or less. Typically, the surface treatment composition forms a surface treatment layer (e.g., a hydrophobic monolayer) on the surface such that the water contact angle of the surface is about 50 degrees or greater.

[0015] In some embodiments, the surface treatment composition may be substantially free of propylene glycol methyl ether acetate and / or substantially free of additional Si-containing compounds other than the at least one trialkylsilyl compound. As used herein, the term "substantially free" refers to a weight percent value of the component of about 0.1% or less (e.g., 0.05% or less, 0.01% or less, 0.005% or less, 0.001% or less, or about 0%).

[0016] In some embodiments, semiconductor substrates that can be treated with the surface treatment compositions described herein are composed of silicon, silicon germanium, silicon nitride, copper, III-V compounds such as GaAs, or any combination thereof. In some embodiments, the semiconductor substrate can be a silicon wafer, a copper wafer, a silicon dioxide wafer, a silicon nitride wafer, a silicon oxynitride wafer, a carbon-doped silicon oxide wafer, a SiGe wafer, or a GaAs wafer. The semiconductor substrate can additionally have exposed integrated circuit structures, such as interconnect features (e.g., metal lines and dielectric materials), on its surface. Metals and alloys used in the interconnect features include, but are not limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, nickel, silicon, polysilicon, titanium nitride, tantalum nitride, tin, tungsten, SnAg, SnAg / Ni, CuNiSn, CuCoCu, and / or CoSn. The semiconductor substrate may also include a dielectric interlayer, a layer of silicon oxide, silicon nitride, titanium nitride, silicon carbide, silicon oxide carbide, silicon oxynitride, titanium oxide, and / or carbon-doped silicon oxide.

[0017] In some embodiments, a semiconductor substrate surface treated with a surface treatment composition described herein contains features comprising SiO2, SiN, TiN, SiOC, SiON, Si, SiGe, Ge, and / or W. In some embodiments, the semiconductor substrate surface contains features comprising SiO2 and / or SiN.

[0018] Typically, the semiconductor substrate surface treated with the surface treatment compositions described herein includes a pattern formed by a prior semiconductor manufacturing process (e.g., a lithographic process including applying a photoresist layer, exposing the photoresist layer to actinic radiation, developing the photoresist layer, etching the semiconductor surface underlying the photoresist layer, and / or removing the photoresist layer). In some embodiments, the pattern includes features having at least one (e.g., two or three) dimensions (e.g., length, width, and / or depth) of about 20 nm or less (e.g., about 15 nm or less, about 10 nm or less, or about 5 nm or less) and / or about 1 nm or more (e.g., about 2 nm or more, or about 5 nm or more).

[0019] Generally, the surface treatment compositions described herein can include at least one (two, three, or four) trialkylsilyl compound and at least one (two, three, or four) solvent. In some embodiments, the trialkylsilyl compound can include a SiR group, where each R is independently a C1-C 16 or C1-C 16 For example, the trialkylsilyl compound may include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, or a tributylsilyl group.

[0020] In some embodiments, the trialkylsilyl compound can be selected from the group consisting of trialkylsilyl alkylsulfonates, trialkylsilyl arylsulfonates, and trialkylsilyl acetates. Suitable examples of trialkylsilyl compounds that can be used in the surface treatment compositions described herein include trialkylsilyl methanesulfonate, trialkylsilyl trifluoromethanesulfonate (e.g., trialkylsilyl triflate), trialkylsilyl perfluorobutanesulfonate, trialkylsilyl p-toluenesulfonate, trialkylsilyl benzenesulfonate, trialkylsilyl trifluoroacetate, trialkylsilyl trichloroacetate, and trialkylsilyl tribromoacetate. A specific example of a suitable trialkylsilyl compound is trimethylsilyl trifluoromethanesulfonate.

[0021] In some embodiments, the at least one trialkylsilyl compound is present in an amount of about 0.1 wt % or more (e.g., about 0.2 wt % or more, about 0.3 wt % or more, about 0.4 wt % or more, about 0.5 wt % or more, about 0.6 wt % or more, about 0.7 wt % or more, about 0.8 wt % or more, about 0.9 wt % or more, about 1 wt % or more, about 2 wt % or more, about 3 wt % or more, about 4 wt % or more, about 5 wt % or more, about 6 wt % or more, about 7 wt % or more, The total amount of the hydroxybenzoates may be from about 8% by weight or more, about 9% by weight or more) to about 15% by weight or less (e.g., about 14% by weight or less, about 13% by weight or less, about 12% by weight or less, about 11% by weight or less, about 10% by weight or less, about 9% by weight or less, about 8% by weight or less, about 7% by weight or less, about 6% by weight or less, about 5% by weight or less, about 4% by weight or less, about 3% by weight or less, about 2% by weight or less, about 1% by weight or less, about 0.9% by weight or less, about 0.8% by weight or less, about 0.7% by weight or less, about 0.6% by weight or less, about 0.5% by weight or less).

[0022] In some embodiments, the surface treatment composition described herein can include at least one solvent (e.g., at least one organic solvent), such as an acid anhydride, a nitrile, a glycol ether, a glycol ether acetate, an alkane, an aromatic hydrocarbon, a sulfone, a sulfoxide, a ketone, an aldehyde, an ester, a lactam, a lactone, an acetal, a hemiacetal, an alcohol, a carboxylic acid (e.g., one having a pKa value of 0 or greater), a sulfonic acid, and an ether. Examples of suitable solvents include acetic anhydride, propionic anhydride, trifluoroacetic anhydride, acetonitrile, C6-C8 16 Alkanes such as toluene, xylene, mesitylene, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dibutyl ether, n-dibutyl ether, anisole, dimethyl sulfone, dimethyl sulfoxide (DMSO), sulfolane, propylene carbonate, methyl ethyl ketone (MEK), cyclohexanone, n-butyl acetate, hexyl acetate, benzyl acetate, amyl acetate, ethyl propionate, ethyl butanoate, propyl propionate, methyl butanoate, acetic acid, formic acid, methanesulfonic acid, trifluoroacetic acid, isobutyl methyl ketone, N-methyl-pyrrolidone (NMP), hydrofluoroethers (e.g., methyl nonafluorobutyl ether and methyl nonafluoroisobutyl ether), or combinations thereof. In some embodiments, the surface treatment compositions described herein may contain water or may be substantially free of water.

[0023] In some embodiments, the at least one solvent may comprise from about 1 wt % or more (e.g., about 5 wt % or more, about 10 wt % or more, about 20 wt % or more, about 30 wt % or more, about 40 wt % or more, about 50 wt % or more, about 60 wt % or more, about 70 wt % or more, about 75 wt % or more, about 80 wt % or more, about 85 wt % or more, about 90 wt % or more, or about 95 wt % or more) to about 99.9 wt % or less (e.g., about 99 wt % or less, about 95 wt % or less, about 90 wt % or less, about 85 wt % or less, about 75 wt % or less, about 65 wt % or less, about 55 wt % or less, about 45 wt % or less, about 35 wt % or less, or about 25 wt % or less) of the surface treatment composition described herein.

[0024] In some embodiments, the surface treatment composition described herein further comprises at least one (e.g., two, three, or four) sulfonic acid or salt thereof. The at least one sulfonic acid can include a sulfonic acid represented by formula (I): R-SO3H, where R is a C1-C4 optionally substituted with one or more (e.g., two, three, or four) halo (e.g., F, Cl, Br, or I). 16 alkyl group (e.g., methyl or octyl), or one or more (e.g., two, three, or four) C1-C 16 Alkyl groups (e.g., C 12 represents a phenyl group optionally substituted with an alkyl group). Examples of suitable sulfonic acids include p-xylene-2-sulfonic acid, p-toluenesulfonic acid, 4-dodecylbenzenesulfonic acid, and 1H,1H,2H,2H-perfluorooctanesulfonic acid. Suitable sulfonate salts include sodium salts, potassium salts, and ammonium salts.

[0025] In some embodiments, the at least one sulfonic acid or salt thereof is present in an amount of about 0.01 wt % or more (e.g., about 0.02 wt % or more, about 0.04 wt % or more, about 0.05 wt % or more, about 0.06 wt % or more, about 0.08 wt % or more, about 0.1 wt % or more, about 0.2 wt % or more, about 0.3 wt % or more, about 0.4 wt % or more, or about 0.5 wt % or more) of the surface treatment composition described herein. ) to about 10% by weight or less (e.g., about 8% by weight or less, about 6% by weight or less, about 5% by weight or less, about 4% by weight or less, about 2% by weight or less, about 1% by weight or less, about 0.9% by weight or less, about 0.8% by weight or less, about 0.7% by weight or less, about 0.6% by weight or less, about 0.5% by weight or less, about 0.4% by weight or less, about 0.3% by weight or less, about 0.2% by weight or less, about 0.1% by weight or less, or about 0.05% by weight or less).

[0026] Surprisingly, it has been found that after a semiconductor substrate surface has been treated with the surface treatment composition described herein, the sulfonic acid or salt thereof can significantly reduce the number of collapsed pattern features (e.g., having dimensions of about 20 nm or less) on the semiconductor substrate surface during drying steps typically used in semiconductor manufacturing processes.

[0027] In some embodiments, when the surface treatment composition described herein includes a Si-containing compound in addition to at least one trialkylsilyl compound, the at least one solvent can include at least one (e.g., two, three, or four) siloxane compound. The siloxane compound can be a disiloxane, oligosiloxane, cyclosiloxane, or polysiloxane. As used herein, the term "oligosiloxane" refers to a compound having 3 to 6 siloxane units, and the term "polysiloxane" refers to a compound having more than 6 siloxane units.

[0028] Suitable examples of siloxane compounds that can be used in the surface treatment composition described in the present disclosure include hexamethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,1-trimethyl-3,3-dimethyldisiloxane, 1,1,3,3-tetra-n-octyldimethyldisiloxane, bis(nonafluorohexyl)tetramethyldisiloxane, 1,3-bis(trifluoropropyl)tetramethyldisiloxane, 1,3-di-n-butyltetramethyldisiloxane, 1,3-di-n-butyltetramethyldisiloxane, 1,3-di-n-butyldimethyl ... Octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, hexa-n-butyldisiloxane, hexaethyldisiloxane, hexavinyldisiloxane, 1,1,1,3,3-pentamethyl-3-acetoxydisiloxane, 1-allyl-1,1,3,3-tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)-tetramethyldisiloxane, 1,3-di Vinyltetraphenyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diallyltetrakis(trimethylsiloxy)disiloxane, 1,3-diallyltetramethyldisiloxane, 1,3-diphenyltetrakis(dimethylsiloxy)disiloxane, (3-chloropropyl)pentamethyldisiloxane, 1,3-divinyltetrakis(trimethylsiloxy)disiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane, 1,1,3,3-tetracyclopentyldisiloxane Chlorodisiloxane, vinylpentamethyldisiloxane, 1,3-bis(3-chloroisobutyl)tetramethyldisiloxane, hexaphenyldisiloxane, 1,3-bis[(bicyclo[2.2.1]hept-2-enyl)ethyl]tetramethyldisiloxane, 1,1,1-triethyl-3,3,3-trimethyldisiloxane, 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane, 1,3-bis(chloromethyl)tetramethyldisiloxane, 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane, 1,1,3,3-Tetraphenyldimethyldisiloxane, methacryloxypentamethyldisiloxane, pentamethyldisiloxane, 1,3-bis(3-chloropropyl)tetramethyldisiloxane, 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane, 1,3-bis(triethoxysilylethyl)tetramethyldisiloxane, 3-aminopropylpentamethyldisiloxane, 1,3-bis(2-aminoethylaminomethyl)-tetramethyldisiloxane, 1,3-bis(3-carboxypropyl)tetramethyldisiloxane, 1,3-dichloro-1,3 -Diphenyl-1,3-dimethyldisiloxane, 1,3-diethynyltetramethyldisiloxane, n-butyl-1,1,3,3-tetramethyldisiloxane, 1,3-dichlorotetraphenyldisiloxane, 1,3-dichlorotetramethyldisiloxane, 1,3-di-t-butyldisiloxane, 1,3-dimethyltetramethoxydisiloxane, 1,3-divinyltetraethoxydisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, vinyl-1,1,3,3-tetramethyldisiloxane, platinum-[1,3-bis(cyclohexyl)methyl] sil)imidazol-2-ylidenehexachlorodisiloxane, 1,1,3,3-tetraisopropyl-1-chlorodisiloxane, 1,1,1-trimethyl-3,3,3-triphenyldisiloxane, 1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane, 3,3-diphenyl-tetramethyltrisiloxane, 3-phenylheptamethyltrisiloxane, hexamethylcyclotrisiloxane, n-propylheptamethyltrisiloxane, 1,5-diethoxyhexamethyltrisiloxane, 3-ethylheptamethyltrisiloxane, 3-( (tetrahydrofurfuryloxypropyl)heptamethyltrisiloxane, 3-(3,3,3-trifluoropropyl)heptamethyltrisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, octamethyltrisiloxane, 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane, hexaphenylcyclotrisiloxane, 1,1,1,5,5,5-hexamethyltrisiloxane, octachlorotrisiloxane, 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane, (3,3,3-trifluoropropyl)methylcyclotrisiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 3-(3-acetoxypropyl)heptamethyltrisiloxane, 3-(m-pentadecylphenoxypropyl)heptamethyltrisiloxane, limonenyltrisiloxane, 3-dodecylheptamethyltrisiloxane, 3-octylheptamethyltrisiloxane, 1,3,5-triphenyltrimethylcyclotrisiloxane , 1,1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,5,5,5-hexaethyl-3-methyltrisiloxane, 1,5-dichlorohexamethyltrisiloxane, 3-triacontylheptamethyltrisiloxane, 3-(3-hydroxypropyl)heptamethyltrisiloxane, hexamethylcyclomethylphosphonoxytrisiloxane, 3-octadecylheptamethyltrisiloxane, furfuryloxytrisiloxane, tetrakis(dimethylsiloxy) Silane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, diphenylsiloxane-dimethylsiloxane copolymer, 1,3-diphenyl-1,3-dimethyldisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane, dimethylsiloxane-[65-70% (60% propylene oxide / 40% ethylene oxide)] block copolymer, bis(hydroxypropyl)tetramethyldisiloxane, tetra-n-propyltetramethylcyclotetrasiloxane siloxane, octaethylcyclotetrasiloxane, decamethyltetrasiloxane, dodecamethylcyclohexasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexaphenylcyclotrisiloxane, polydimethylsiloxane, polyoctadecylmethylsiloxane, hexacosyl-terminated polydimethylsiloxane, decamethylcyclopentasiloxane, poly(3,3,3-trifluoropropylmethylsiloxane), trimethylsiloxy-terminated polydimethylsiloxane, 1,1,3,3,5,5,7,7,9,Includes 9-decamethylpentasiloxane and triethylsiloxy-terminated polydiethylsiloxane.

[0029] In some embodiments, the at least one siloxane compound is present in an amount of about 0.1% by weight or more (e.g., about 1% by weight or more, about 5% by weight or more, about 10% by weight or more, about 20% by weight or more, about 30% by weight or more, about 40% by weight or more, about 50% by weight or more, about 60% by weight or more, about 70% by weight or more, about 80% by weight or more, about 90% by weight or more, about 91% by weight or more, about 93% by weight or more, The total weight of the cellulose acetate solution may be from about 95% by weight or more, about 97% by weight or more, or about 99% by weight or more) to about 99.9% by weight or less (e.g., about 99% by weight or less, about 98% by weight or less, about 96% by weight or less, about 94% by weight or less, about 92% by weight or less, about 90% by weight or less, about 85% by weight or less, about 80% by weight or less, about 75% by weight or less, about 70% by weight or less, about 65% by weight or less, about 60% by weight or less, about 55% by weight or less, or about 50% by weight or less).

[0030] In some embodiments, the surface treatment compositions described herein may include only two types of components, such as (1) at least one trialkylsilyl compound and (2) at least one solvent (e.g., a siloxane compound). In some embodiments, the surface treatment compositions described herein may include only three types of components, such as (1) at least one trialkylsilyl compound, (2) at least one sulfonic acid, and (3) at least one solvent.

[0031] Without intending to be bound by theory, it is believed that the surface treatment compositions described herein can form a surface treatment layer (e.g., a hydrophobic layer such as a hydrophobic monolayer) on the patterned surface of a semiconductor substrate such that the water contact angle of the patterned surface of the semiconductor substrate is about 50 degrees or more (e.g., 55 degrees or more, 60 degrees or more, 65 degrees or more, 70 degrees or more, 75 degrees or more, 80 degrees or more, 85 degrees or more, 89 degrees or more, 90 degrees or more, 95 degrees or more, or 100 degrees or more) and / or 175 degrees or less. Without intending to be bound by theory, it is believed that such a surface treatment layer can prevent or minimize collapse of pattern features (e.g., features having dimensions of about 20 nm or less) on the semiconductor substrate surface during drying steps commonly used in semiconductor production processes after the semiconductor substrate surface has been treated with the surface treatment composition described herein.

[0032] In some embodiments, the surface treatment compositions described herein may exclude or be substantially free of one or more additives (in any combination of multiple additives). Such compounds may include non-aromatic hydrocarbons, protic solvents (e.g., alcohols or amides), lactones (e.g., 5- or 6-membered rings), propylene glycol methyl ether acetate, Si-containing compounds (e.g., siloxanes such as disiloxanes; silanes; silazanes such as disilazanes, cyclic silazanes, or heterocyclic silazanes; and those containing Si-H or aminosilyl groups), polymers, oxygen scavengers, quaternary ammonium salts, including quaternary ammonium hydroxides, amines, bases (e.g., alkane, alkane, alkane-based silazanes ... Potassium bases (e.g., NaOH, KOH, LiOH, Mg(OH)2, and Ca(OH)2), surfactants, antifoaming agents, fluorine-containing compounds (e.g., HF, H2SiF6, H2PF6, HBF4, NHF, and tetraalkylammonium fluorides), oxidizing agents (e.g., peroxide, hydrogen peroxide, ferric nitrate, potassium iodate, potassium permanganate, nitric acid, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, peroxide, and peracetic acid), abrasives, silicates, hydroxycarboxylic acids, carboxylic acids and polycarboxylic acids without amino groups, silanes (e.g., alkoxysilanes), cyclic compounds other than the cyclosiloxanes described herein (e.g., cyclic compounds containing at least two rings, such as unsubstituted or substituted naphthalene or unsubstituted or substituted biphenyl ether), chelating agents (e.g., azoles, diazoles, triazoles, or tetraazoles), corrosion inhibitors (e.g., azole or non-azole corrosion inhibitors), buffering agents, guanidines, guanidine salts, pyrrolidones, polyvinylpyrrolidones, metal halides, and metal-containing catalysts.

[0033] In some embodiments, the surface treatment methods described herein may further include contacting the surface of the semiconductor substrate with at least one aqueous cleaning solution prior to contacting the surface with the surface treatment composition, wherein the at least one aqueous cleaning solution comprises water, an alcohol, an aqueous ammonium hydroxide solution, an aqueous hydrochloric acid solution, an aqueous hydrogen peroxide solution, an organic solvent, or a combination thereof.

[0034] In some embodiments, the surface treatment method described herein may further include contacting the surface of a substrate with a first rinse liquid (e.g., water, an organic solvent such as isopropanol, or a combination thereof) after contacting the surface with the at least one aqueous cleaning liquid but before contacting the surface with the surface treatment composition. In some embodiments, the surface treatment method described herein may further include contacting the surface with a second rinse liquid (e.g., water, an organic solvent such as isopropanol, or a combination thereof) after contacting the surface with the surface treatment composition. In some embodiments, the surface treatment method described herein may further include drying the surface (e.g., after either contacting the surface with the first rinse liquid, contacting the surface with the surface treatment composition, or contacting the surface with the second rinse liquid). In some embodiments, the surface treatment method described herein may further include removing a surface treatment layer from the surface.

[0035] In some embodiments, the present disclosure provides a method for cleaning a semiconductor substrate (e.g., a wafer) having a pattern disposed on the surface of the substrate, the method being carried out, for example, by: a) optionally contacting the surface with an aqueous cleaning solution; b) optionally contacting the surface with a first rinse solution; c) contacting the surface with a surface treatment composition comprising at least one trialkylsilyl compound and at least one solvent, such that the surface treatment composition forms a surface treatment layer on the surface such that the surface has a water contact angle of about 50 degrees or greater; d) optionally contacting the surface with a second rinse; e) drying the surface; and f) Optionally, removing the surface treatment layer to form a clean, patterned surface. In such embodiments, the pattern may include features with dimensions of about 20 nm or less.

[0036] In step a) of the above method, the substrate (e.g., wafer) with a patterned surface may optionally be treated with one or more aqueous cleaning solutions. When the patterned surface is treated with two or more aqueous cleaning solutions, the cleaning solutions may be applied sequentially. The aqueous cleaning solution may be water alone, an organic solvent alone, or a solution containing water, a solute, and, optionally, an organic solvent. In some embodiments, the aqueous cleaning solution may include water, an alcohol (e.g., a water-soluble alcohol such as isopropanol), an aqueous ammonium hydroxide solution, an aqueous hydrochloric acid solution, a hydrogen peroxide solution, an organic solvent (e.g., a water-soluble organic solvent), or a combination thereof.

[0037] In step b), the cleaning solution from step a) may optionally be rinsed away with a first rinse solution. The first rinse solution may comprise water, an organic solvent (e.g., isopropanol), or an aqueous solution containing an organic solvent. In some embodiments, the first rinse solution is at least partially miscible with the cleaning solution used in step a). In some embodiments, if the cleaning solution used in step a) is not moisture sensitive or does not contain an appreciable amount of water, step b) can be omitted.

[0038] In step c), the substrate surface can be treated with the surface treatment composition disclosed above to form a modified surface having a surface treatment layer (e.g., a hydrophobic layer). The modified surface thus formed is hydrophobic and has a water contact angle of about 50 degrees or greater. In some embodiments, the contact angle is about 55 degrees or greater (e.g., about 60 degrees or greater, about 65 degrees or greater, about 70 degrees or greater, about 75 degrees or greater, about 80 degrees or greater, about 85 degrees or greater, about 90 degrees or greater, about 95 degrees or greater, or about 100 degrees or greater) and / or at most about 175 degrees. In some embodiments, this step can be performed at a temperature of about 20-35°C for a process time ranging from about 10 seconds to about 300 seconds.

[0039] In step d), after the substrate surface has been treated with the surface treatment composition, the surface may be rinsed with a second rinse solution. The second rinse solution may include water, an organic solvent (e.g., isopropanol), or an aqueous solution containing an organic solvent. In some embodiments, this step may be performed at a temperature of 20 to 70°C.

[0040] In step e), the substrate surface may be dried (e.g., using pressurized gas). Without intending to be bound by theory, it is believed that after the substrate surface has been treated with the surface treatment composition described herein, this drying step minimizes surface pattern collapse.

[0041] In step f), after the drying step, the surface treatment layer (e.g., the hydrophobic layer) may optionally be removed. Generally, the surface treatment layer can be removed by various methods depending on the chemical nature of the modified surface. Suitable methods for removing the surface treatment layer include plasma sputtering; plasma ashing; heat treatment at atmospheric or subatmospheric pressure; treatment with an acid, base, oxidizing agent, or solvent containing a condensed fluid (e.g., a supercritical fluid such as supercritical CO2); gas or liquid treatment; UV irradiation; or a combination thereof.

[0042] The semiconductor substrate having a clean, patterned surface obtained by the above method may be further processed to form one or more circuits on the substrate, for example, by assembling (e.g., dicing and bonding) and packaging (e.g., chip sealing), or may be processed into a semiconductor device (e.g., an integrated circuit such as a semiconductor chip).

[0043] In some embodiments, the present disclosure provides articles (e.g., intermediate semiconductor articles formed during the manufacture of semiconductor devices) comprising a semiconductor substrate and a surface treatment composition described herein supported on the semiconductor substrate. The surface treatment composition may include at least one trialkylsilyl compound and at least one solvent, as described above.

[0044] In some embodiments, the present disclosure features a kit comprising a first container containing at least one trialkylsilyl compound and a second container containing at least one solvent. Optionally, the first or second container may further contain at least one organic solvent to form a solution containing the components in each container. In some embodiments, the components in the first and second containers may be mixed to form a surface treatment composition at the point of use just before applying the surface treatment composition to the surface of a semiconductor substrate. While not intending to be bound by theory, such a method is believed to be particularly suitable for surface treatment compositions with a relatively short shelf life. In embodiments where the surface treatment composition has a relatively long shelf life, the components in the first and second containers may be mixed to form a solution, which can be stored for a relatively long period of time before use.

[0045] The present disclosure is illustrated in more detail by the following examples, which are for illustrative purposes and should not be construed as limiting the scope of the present disclosure. [Example]

[0046] Example 1 Surface treatment solutions (e.g., Formulations 1-16) were prepared by mixing the ingredients at room temperature. The compositions of Formulations 1-16 are summarized in Table 1 below. All percentages listed in Table 1 are by weight unless otherwise noted.

[0047] Semiconductor substrates containing SiO2 films were treated with Formulations 1-16, and the contact angles of the treated surfaces were measured as follows. Coupons with SiO2 films on Si substrates were cut into 1-inch squares and washed with isopropanol at room temperature for 30 seconds. The coupons were immersed vertically in 100 mL of the stirred (50 RPM) surface treatment solution and held at room temperature for 30 seconds. The coupons were then rinsed with isopropanol at 50°C for 60 seconds and dried using pressurized nitrogen gas.

[0048] The coupon was placed in an AST VCA 3000 Contact Angle Tool and the contact angle was measured using the following procedure: 1. Place the SiO2 coupon on the stage. 2. Turn the vertical knob clockwise to raise the stage until the sample is directly below the needle. 3. Dispense a drop of deionized water, lightly touch the sample surface, and allow the sample to process until the drop comes off the tip of the needle. 4. Use the level knob on the stage adjustment to center the drop in the field of view. 5. Move the stage along the guide rails to focus on the droplet in the field of view and obtain a sharp image. 6. Click the "AutoFAST" button to freeze the image and calculate. Two numbers will be displayed; these are the left and right contact angles. 7. To perform a manual calculation, use the mouse to place five markers around the drop. 8. Select the drop icon from the Main Menu and calculate the contact angle. 9. This will create a curve fit and a tangent to the image. Two numbers will appear in the left corner of the screen; these are the left and right contact angles. 10. The above procedure was carried out for three substrate sites, and the resulting contact angles were averaged. The average results are shown in Table 1.

[0049] [Table 1]

[0050] As shown in Table 1, Formulations 1-8, 10, 11, and 13-18 (which contain a trimethylsilyl compound and at least one suitable solvent) exhibited relatively large contact angle values ​​on the SiO2 surface.

[0051] Example 2 Surface treatment solutions (e.g., Formulations 19-44) were prepared by mixing the ingredients at room temperature. The compositions of Formulations 19-44 are summarized in Tables 2-5 below. All percentages in Tables 2-5 are by weight unless otherwise noted.

[0052] Semiconductor substrates containing SiO2 films were treated with Formulations 19-44. The contact angles of the treated surfaces were measured as described in Example 1. The number of intact features was determined from SEM photographs of the treated substrates.

[0053] [Table 2]

[0054] As shown in Table 2, Formulations 19-22 (each containing sulfonic acid) surprisingly exhibit a higher percentage of intact features compared to Formulation 17 (which does not contain sulfonic acid).

[0055] [Table 3]

[0056] Stiffness is the ability of Si pillars on patterned wafers to resist bending, expressed as a force in mN / m. Table 3 shows the properties of Formulations 23-37 as a function of Si pillar stiffness. As shown in Table 3, Si pillars with lower stiffness tend to collapse more easily when subjected to stress during drying compared to those with higher stiffness.

[0057] [Table 4]

[0058] Table 4 shows the performance of Formulations 38-41 as a function of trimethylsilyl triflate concentration. As shown in Table 4, higher concentrations of trimethylsilyl triflate generally resulted in a higher percentage of intact features.

[0059] [Table 5]

[0060] Table 5 shows the performance of Formulations 42-44 using different rinse solutions. As shown in Table 5, a relatively high percentage of intact features was achieved with all three rinse solutions tested.

[0061] Other embodiments are within the scope of the following claims.

[0062] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority from U.S. Provisional Patent Application No. 62 / 820,905, filed March 20, 2019, U.S. Provisional Patent Application No. 62 / 756,644, filed November 7, 2018, and U.S. Provisional Patent Application No. 62 / 712,006, filed July 30, 2018, the disclosures of which are incorporated herein by reference in their entireties.

Claims

1. 1. A method for processing a semiconductor substrate having a pattern disposed on a surface of the wafer, comprising: contacting the surface with a liquid surface treatment composition to form a surface treatment layer such that the water contact angle of the surface treatment layer is about 50 degrees or more, wherein the surface treatment composition comprises at least one siloxane compound and at least one trialkylsilyl compound selected from the group consisting of trialkylsilyl alkyl sulfonates, trialkylsilyl aryl sulfonates, and trialkylsilyl acetates; Including, the pattern includes features with dimensions of about 20 nm or less; The method.

2. The at least one trialkylsilyl compound is SiR ３ group, each R independently being selected from the group １ ~C １６ alkyl or C １ ~C １６ The method of claim 1 , wherein the haloalkyl is

3. 2. The method of claim 1, wherein the at least one trialkylsilyl compound comprises a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, or a tributylsilyl group.

4. 2. The method of claim 1, wherein the at least one trialkylsilyl compound comprises trialkylsilyl methanesulfonate, trialkylsilyl trifluoromethanesulfonate, trialkylsilyl perfluorobutanesulfonate, trialkylsilyl p-toluenesulfonate, trialkylsilyl benzenesulfonate, trialkylsilyl trifluoroacetate, trialkylsilyl trichloroacetate, or trialkylsilyl tribromoacetate.

5. 10. The method of claim 1, wherein the at least one trialkylsilyl compound is from about 0.1% to about 15% by weight of the surface treatment composition.

6. The method of claim 1 , wherein the at least one siloxane compound comprises a disiloxane, an oligosiloxane, a cyclosiloxane, or a polysiloxane.

7. The at least one siloxane compound is selected from the group consisting of hexamethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,1-triethyl-3,3-dimethyldisiloxane, 1,1,3,3-tetra-n-octyldimethyldisiloxane, bis(nonafluorohexyl)tetramethyldisiloxane, 1,3-bis(trifluoropropyl)tetramethyldisiloxane, disiloxane, 1,3-di-n-butyltetramethyldisiloxane, 1,3-di-n-octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, hexa-n-butyldisiloxane, hexaethyldisiloxane, hexavinyldisiloxane, 1,1,1,3,3-pentamethyl-3-acetoxydisiloxane, 1-allyl-1,1,3,3-tetramethyldisiloxane Siloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane, 1,3-divinyltetraphenyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diallyltetrakis(trimethylsiloxy)disiloxane, 1,3-diallyltetramethyldisiloxane, 1,3-diphenyltetrakis Tetrakis(dimethylsiloxy)disiloxane, (3-chloropropyl)pentamethyldisiloxane, 1,3-divinyltetrakis(trimethylsiloxy)disiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane, 1,1,3,3-tetracyclopentyldichlorodisiloxane, vinylpentamethyldisiloxane, 1,3-bis(3-chloroisobutyl)tetra Methyldisiloxane, hexaphenyldisiloxane, 1,3-bis[(bicyclo[2.2.1]hept-2-enyl)ethyl]tetramethyldisiloxane, 1,1,1-triethyl-3,3,3-trimethyldisiloxane, 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane, 1,3-bis(chloromethyl)tetramethyldisiloxane, 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane, 1,1,3,3-tetraphenyldimethyldisiloxane, methacryloxypentamethyldisiloxane, pentamethyldisiloxane, 1,3-bis(3-chloropropyl)tetramethyldisiloxane, 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane, 1,3-bis(triethoxysilylethyl)tetramethyldisiloxane, 3-aminopropylpentamethyldisiloxane tetramethyldisiloxane, 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane, 1,3-bis(3-carboxypropyl)tetramethyldisiloxane, 1,3-dichloro-1,3-diphenyl-1,3-dimethyldisiloxane, 1,3-diethynyltetramethyldisiloxane, n-butyl-1,1,3,3-tetramethyldisiloxane, 1,3-dichlorotetraphenyl Disiloxane, 1,3-dichlorotetramethyldisiloxane, 1,3-di-t-butyldisiloxane, 1,3-dimethyltetramethoxydisiloxane, 1,3-divinyltetraethoxydisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, vinyl-1,1,3,3-tetramethyldisiloxane, platinum-[1,3-bis(cyclohexyl)imidazol-2-ylidene Hexachlorodisiloxane, 1,1,3,3-tetraisopropyl-1-chlorodisiloxane, 1,1,1-trimethyl-3,3,3-triphenyldisiloxane, 1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane, 3,3-diphenyltetramethyltrisiloxane, 3-phenylheptamethyltrisiloxane, hexamethylcyclotrisiloxane, n-propylheptamethyltrisiloxane, 1,5-diethoxyhexamethyltrisiloxane, 3-ethylheptamethyltrisiloxane, 3-(tetrahydrofurfuryloxypropyl)heptamethyltrisiloxane, 3-(3,3,3-trifluoropropyl)heptamethyltrisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, octamethyltrisiloxane, 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane, hexaphenylcyclotrisiloxane, 1,1,1,5,5,5-hexamethyltrisiloxane, octachlorotrisiloxane, 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane methylcyclotrisiloxane, (3,3,3-trifluoropropyl)methylcyclotrisiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 3-(3-acetoxypropyl)heptamethyltrisiloxane, 3-(m-pentadecylphenoxypropyl)heptamethyltrisiloxane, limonenyltrisiloxane, 3-dodecylheptamethyltrisiloxane, 3- Octylheptamethyltrisiloxane, 1,3,5-triphenyltrimethylcyclotrisiloxane, 1,1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,5,5,5-hexaethyl-3-methyltrisiloxane, 1,5-dichlorohexamethyltrisiloxane, 3-triacontylheptamethyltrisiloxane, 3-(3-hydroxypropyl)heptamethyltrisiloxane silane, hexamethylcyclomethylphosphonoxytrisiloxane, 3-octadecylheptamethyltrisiloxane, furfuryloxytrisiloxane, tetrakis(dimethylsiloxy)silane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, diphenylsiloxane-dimethylsiloxane copolymer, 1,3-diphenyl-1,3-dimethyldisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane, dimethylsiloxane-[65-70% (60% propylene oxide / 40% ethylene oxide)] block copolymer, bis(hydroxypropyl)tetramethyldisiloxane, tetra-n-propyltetramethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, decamethyltetrasiloxane, dodecamethylcyclohexasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, , hexaphenylcyclotrisiloxane, polydimethylsiloxane, polyoctadecylmethylsiloxane, hexacosyl-terminated polydimethylsiloxane, decamethylcyclopentasiloxane, poly(3,3,3-trifluoropropylmethylsiloxane), trimethylsiloxy-terminated polydimethylsiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, or triethylsiloxy-terminated polydiethylsiloxane.

8. The method of claim 1 , wherein the at least one siloxane compound is from about 85% to about 99.9% by weight of the surface treatment composition.

9. 10. The method of claim 1, further comprising contacting the surface with at least one aqueous cleaning fluid prior to contacting the surface with the surface treatment composition.

10. 10. The method of claim 9, wherein the at least one aqueous cleaning solution comprises water, an alcohol, an aqueous ammonium hydroxide solution, an aqueous hydrochloric acid solution, an aqueous hydrogen peroxide solution, an organic solvent, or a combination thereof.

11. 10. The method of claim 9, further comprising contacting the surface with a first rinse liquid after contacting the surface with the at least one aqueous cleaning liquid and before contacting the surface with the surface treatment composition.

12. 10. The method of claim 1, further comprising contacting the surface with a second rinse after contacting the surface with the surface treatment composition.

13. The method of claim 1 further comprising drying the surface.

14. The method of claim 1 further comprising removing the surface treatment layer.

15. The surface is SiO ２ , SiN, TiN, SiOC, SiON, Si, SiGe, Ge, or W.

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