WO2020071608A1 - Surface treatment composition and surface treatment method using same - Google Patents

Abstract

The present invention relates to a surface treatment composition and a surface treatment method using same. A surface treatment composition according to one aspect of the present invention comprises a chelating agent, a nonionic surfactant, an anionic surfactant, and a pH controller. In addition, a surface treatment method, according to another aspect of the present invention, performs surface treatment on a wafer for a semiconductor device by using the surface treatment composition, according to one aspect of the present invention, after the wafer for a semiconductor device is chemical mechanical polished.

Description

Surface treatment composition and surface treatment method using same

The present invention relates to a surface treatment composition, and relates to a surface treatment composition and a surface treatment method using the same, which are used in a surface treatment process performed after a chemical mechanical polishing process of a wafer for semiconductor devices and before a cleaning process.

Microelectronic device wafers are used to form integrated circuits. The microelectronic device wafer includes a wafer, such as silicon, into which the regions for deposition of different materials having insulating, conductive or semiconducting properties are patterned. To obtain accurate patterning, the excess material used to form the layers on the wafer must be removed. In addition, in order to fabricate functional and reliable circuits, it is important to fabricate flat or flat microelectronic wafer surfaces prior to subsequent processing. Therefore, it is necessary to remove and / or polish certain surfaces of microelectronic device wafers.

Chemical mechanical polishing (CMP) is a process in which any material is removed from the surface of a microelectronic device wafer, and the surface is polished in cooperation with a chemical process such as oxidation or chelating a physical process such as polishing. In its most basic form, CMP involves applying a slurry, eg, a solution of an abrasive and an active compound, to a polishing pad that buffs the surface of a microelectronic device wafer to achieve a removal, planarization and polishing process. In the manufacture of integrated circuits, CMP slurries should also be capable of preferentially removing films comprising composite layers of metal and other materials such that highly flat surfaces can be created for subsequent lithography or patterning, etching and thin film processing. .

Meanwhile, a cleaning process may be performed in order to remove particles, metal atoms, organic substances, and the like generated in the manufacturing process of the semiconductor device and to improve device reliability. However, in general, since the cleaning liquid composition used for cleaning after polishing is rich in OH- in an alkaline aqueous solution, it is easy to remove the abrasive particles through electrical repulsion by charging the abrasive particles and the wafer surface. There is a problem in that impurities such as metal contaminants and organic residues on the wafer surface after cleaning are not effectively removed. In addition, when the pH of the cleaning liquid composition is 8 or more, roughness tends to occur on the wafer surface by the etching action with the basic compound. Accordingly, there is a need for a composition used for surface treatment prior to a cleaning process that can effectively remove residual particles, organic contaminants, and metal contaminants while minimizing surface damage.

The present invention is to solve the above-mentioned problems, the object of the present invention is to minimize the damage to the surface in the surface treatment process performed after the chemical mechanical polishing of the wafer for semiconductor devices, by changing the surface characteristics of defects in the subsequent cleaning process, It is to provide a surface treatment composition capable of removing residual particles, organic contaminants and metal contaminants and a surface treatment method using the same.

However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

In one aspect of the invention, the chelating agent; Nonionic surfactants; Anionic surfactants; And a pH adjusting agent.

In one aspect, the chelating agent may be an organic acid, a compound containing a phosphate group, or both.

In one aspect, the organic acid, a linear saturated carboxylic acid having one carboxyl group; Saturated aliphatic dicarboxylic acid; Unsaturated aliphatic dicarboxylic acid; Aromatic dicarboxylic acids; And at least one selected from the group consisting of carboxylic acids having three or more carboxyl groups, and the linear saturated carboxylic acid having one carboxyl group is formic acid, acetic acid, Propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid (decanoic acid), undecylenic acid, lauric acid, tridecylic acid, myristic acid, pentadecanoic acid and palmitic acid ), Wherein the saturated aliphatic dicarboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, ah. Adipic acid, pimelic acid, water And at least one selected from the group consisting of suberic acid, azelaic acid, and sebacic acid, and the unsaturated aliphatic dicarboxylic acid is maleic acid, fumaric acid. acid), glutaconic acid (glutaconic acid), traumatic acid (traumatic acid) and at least one selected from the group consisting of muconic acid (muconic acid), the aromatic dicarboxylic acid, phthalic acid (phthalic acid), A carboxylic acid having at least one selected from the group consisting of isophthalic acid and terephthalic acid, and having three or more carboxyl groups, citric acid, isocitric acid, acon Contains at least one selected from the group consisting of aconitic acid, carballylic acid, tribasic acid, and mellitic acid It may be.

In one aspect, the compound containing the phosphate group is selected from the group consisting of phosphate ion (3 base), hydrogen phosphate ion (2 base), dihydrogen phosphate (1 base) and trihydrogen phosphate (acid) It may be to include at least any one.

In one aspect, the compound containing the phosphate group is ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropylidene-1,1 ' -Diphosphonic acid, 1-hydroxybutylidene-1,1'-diphosphonic acid, ethylaminobis (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), 2-phosphono-butane-1, 2,4-tricarboxylic acid (2-phosphono-butane-1,2,4-tricarboxylic acid, PBTC), nitrilotris (methylenephosphonic acid) (NTPO), ethylenediaminebis (methylenephosphonic acid) (EDDPO) , 1,3-propylenediaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) (EDTPO), ethylenediaminetetra (ethylenephosphonic acid), 1,3-propylenediaminetetra (methylenephosphonic acid) (PDTMP) , 1,2-diaminopropanetetra (methylenephosphonic acid), 1,6-hexamethylenediaminetetra (methylenephosphonic acid), hexenediaminetetra (methylenephosphonic acid), diethylenetriamine pen (Methylenephosphonic acid) (DEPPO), diethylenetriaminepentakis (methylphosphonic acid), N, N, N ', N'-ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (ethylenephosphonic acid) , Triethylenetetramine hexa (methylene phosphonic acid) and triethylene tetramine hexa (ethylene phosphonic acid) may include at least one selected from the group consisting of.

In one aspect, the chelating agent may be 0.5 to 5% by weight of the surface treatment composition.

In one aspect, the nonionic surfactant is at least selected from the group consisting of alkoxylate surfactants, fatty acid ester surfactants, amide surfactants, alcohol surfactants, ethylenediamine surfactants and silicone surfactants It may include any one.

In one aspect, the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether (alkyl C ₈ ~ C ₁₈ ), polyoxy Ethylene polyoxypropylene copolymer, polyoxyethylene stearyl amine, sorbitan fatty acid ester, glycerin fatty acid ester, primary alcohol ethoxylate, phenol ethoxylate, nonylphenol ethoxylate, octylphenol ethoxylate, lauryl Alcohol ethoxylate, oleyl alcohol ethoxylate, fatty acid ester-based, amide-based, natural alcohol-based, ethylenediamine-based, at least one selected from the group consisting of secondary alcohol ethoxylate-based and alkyl glucoside May be

In one aspect, the nonionic surfactant may be 0.3 wt% to 3 wt% of the surface treatment composition.

In one side, the anionic surfactant, sulfonic acid group (-SO ₃ H), carboxyl group (-COOH), phosphonic group (-PO ₃ H ₂ ), phosphinic group (-HPO ₂ H), sulfate ester (-O · SO ₃ H), fatty acid ions (-COO-), sulfate ions (-OSO _3- ) and sulfite ions (-SO _3- ) may include at least one selected from the group consisting of.

In one aspect, the anionic surfactant, alkylbenzenesulfonic acid, alkylsulfonic acid, alkanesulfonic acid, alkylarylsulfonic acid, polystyrenesulfonic acid, alpha-olefinsulfonic acid, dodecylbenzenesulfonic acid, alkyl sulfate, alkyl ether sulfate ( alkyl ether sulfate), alkyl sulfate esters, alkyl ether sulfate esters, polyoxyethylene lauryl ether acetic acid, polyoxyethylene tridecyl ether carboxylic acid, polyoxyethylene lauryl ether phosphoric acid, polyoxyethylene arylphenyl ether phosphate and their It may be to include at least one selected from the group consisting of salts.

In one aspect, the anionic surfactant may be from 0.01% to 3% by weight of the surface treatment composition.

In one aspect, the content ratio of the nonionic surfactant / anionic surfactant may be 0.75 or less.

In one aspect, the pH adjusting agent, monoethanolamine, methylethanolamine, ethylethanolamine, diethanolamine, triethanolamine and N-amino-N-propanol, methylamine, dimethylamine, trimethylamine, ethylamine, di Ethylamine, triethylamine, ethylenediamine, monoethanolamine, N- (β-aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine anhydride, piperazine Hexahydrate, 1- (2-aminoethyl) piperazine and N-methylpiperazine, ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonium hydrogencarbonate, ammonium carbonate, potassium hydrogencarbonate, carbonic acid Potassium, sodium hydrogen carbonate, sodium carbonate, ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, hydrogen carbonate Cerium, it may be one containing at least one selected from the group consisting of potassium carbonate, sodium bicarbonate and sodium carbonate.

In one side, the pH of the surface treatment composition may be 2 to 7.

In one aspect, the surface treatment composition, the silicon nitride film, silicon oxide film, polysilicon film and at least one film selected from the group consisting of silicon film for removing the defects, residues and contaminants on the wafer surface for semiconductor devices May be

In one aspect, the amount of change in the contact angle of water with respect to the wafer surface for semiconductor devices surface-treated with the surface treatment composition and the contact angle of water with respect to the wafer surface for semiconductor devices before surface treatment may be 2 ° to 7 °.

In one aspect, when surface-treated with the surface treatment composition, the defect reduction rate for the silicon nitride film may be 80% or more, and the defect reduction rate for the polysilicon film may be 75% or more.

In another aspect of the present invention, using the surface treatment composition according to an aspect of the present invention, to provide a surface treatment method, the semiconductor device wafer after the chemical mechanical polishing of the wafer for semiconductor devices.

The surface treatment composition according to one aspect of the present invention chemically buffs the wafer surface for a semiconductor device after chemical mechanical polishing of the wafer for semiconductor devices to change the surface properties, and facilitates cleaning and defect removal in subsequent cleaning processes Do. In addition, contaminants such as abrasive particles, organic substances, and impurities remaining after polishing of the semiconductor wafer can be sufficiently removed.

By the surface treatment method according to another aspect of the present invention, defects can be easily removed in a subsequent cleaning process by changing the wafer surface properties for semiconductor devices after chemical mechanical polishing.

1 is a photograph showing a water contact angle measurement on the surface of the SiN wafer according to the surface treatment composition of Test Examples 1 to 4 of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, various changes may be made to the embodiments, and the scope of the patent application right is not limited or limited by these embodiments. It should be understood that all modifications, equivalents, or substitutes for the embodiments are included in the scope of rights.

The terms used in the examples are for illustrative purposes only and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, the terms "include" or "have" are intended to indicate the presence of features, numbers, steps, actions, components, parts or combinations thereof described herein, one or more other features. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person skilled in the art to which the embodiment belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having meanings consistent with meanings in the context of related technologies, and should not be interpreted as ideal or excessively formal meanings unless explicitly defined in the present application. Does not.

In addition, in the description with reference to the accompanying drawings, the same reference numerals are assigned to the same components regardless of reference numerals, and redundant descriptions thereof will be omitted. In describing the embodiments, when it is determined that detailed descriptions of related known technologies may unnecessarily obscure the subject matter of the embodiments, detailed descriptions thereof will be omitted.

In one aspect of the invention, the chelating agent; Nonionic surfactants; Anionic surfactants; And a pH adjusting agent.

The surface treatment composition according to an aspect of the present invention serves to change the surface properties by chemically buffing the surface of a wafer for a chemical mechanically polished semiconductor device, and facilitates cleaning and defect removal in subsequent cleaning processes. Do it.

As an example of the present invention, the chelating agent helps to prevent redeposition of the removed metal to the semiconductor surface.

In one aspect, the chelating agent may be an organic acid, a compound containing a phosphate group, or both.

As an example of the present invention, the organic acid may have a function of a pH buffering agent in the surface treatment composition, and provide a cleaning effect of abrasive particles, organic substances, impurities, etc. remaining after the polishing process.

In one aspect, the organic acid, a linear saturated carboxylic acid having one carboxyl group; Saturated aliphatic dicarboxylic acid, unsaturated aliphatic dicarboxylic acid; Aromatic dicarboxylic acids; And carboxylic acid having three or more carboxyl groups; may include at least any one selected from the group consisting of, it may be preferably a carboxylic acid having three or more carboxyl groups.

In one aspect, the linear saturated carboxylic acid having one carboxyl group, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, undecylenic acid, lauric acid , Tridecylic acid, myristic acid, pentadecanoic acid, and palmitic acid.

In one aspect, the saturated aliphatic dicarboxylic acid, oxalic acid (oxalic acid), malonic acid (malonic acid), succinic acid (succinic acid), glutaric acid (glutaric acid), adipic acid (adipic acid), pimelic acid (pimelic acid), suberic acid (suberic acid), azelaic acid (azelaic acid) and sebacic acid (sebacic acid) may include at least one selected from the group consisting of.

In one aspect, the unsaturated aliphatic dicarboxylic acid, maleic acid (maleic acid), fumaric acid (fumaric acid), glutaconic acid (glutaconic acid), traumatic acid (traumatic acid) and muconic acid (muconic acid) in the group consisting of It includes at least any one selected, and the aromatic dicarboxylic acid may include at least one selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid.

In one aspect, the carboxylic acid having three or more carboxyl groups, citric acid, isocitric acid, aconic acid, carballylic acid, tribasic acid ) And may be one comprising at least one selected from the group consisting of melitic acid.

As an example of the present invention, the compound containing the phosphate group may increase the removal effect of abrasive particles and metal impurities remaining on the wafer for semiconductor devices.

In one aspect, the compound containing the phosphate group is selected from the group consisting of phosphate ion (3 base), hydrogen phosphate ion (2 base), dihydrogen phosphate (1 base) and trihydrogen phosphate (acid) It may be to include at least any one.

In one aspect, the compound containing the phosphate group is ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropylidene-1,1 ' -Diphosphonic acid, 1-hydroxybutylidene-1,1'-diphosphonic acid, ethylaminobis (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), 2-phosphono-butane-1, 2,4-tricarboxylic acid (2-phosphono-butane-1,2,4-tricarboxylic acid, PBTC), nitrilotris (methylenephosphonic acid) (NTPO), ethylenediaminebis (methylenephosphonic acid) (EDDPO) , 1,3-propylenediaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) (EDTPO), ethylenediaminetetra (ethylenephosphonic acid), 1,3-propylenediaminetetra (methylenephosphonic acid) (PDTMP) , 1,2-diaminopropanetetra (methylenephosphonic acid), 1,6-hexamethylenediaminetetra (methylenephosphonic acid), hexenediaminetetra (methylenephosphonic acid), diethylenetriamine pen (Methylenephosphonic acid) (DEPPO), diethylenetriaminepentakis (methylphosphonic acid), N, N, N ', N'-ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (ethylenephosphonic acid) , Triethylenetetramine hexa (methylene phosphonic acid) and triethylene tetramine hexa (ethylene phosphonic acid) may include at least one selected from the group consisting of.

In one aspect, the chelating agent may be 0.5 to 5% by weight of the surface treatment composition. When the chelating agent is less than 0.5% by weight of the surface treatment composition, the solubility in metal oxide tends to be low, and when it exceeds 5% by weight, the surface treatment composition may be corroded or dissolved in metal parts such as metal wiring. have.

On one side, the nonionic surfactant is easy to remove organics and improves cleaning and defects for hydrophobic films such as polysilicon. The nonionic surfactant is hydrophilic and has a property of being well soluble in water, so it is easy to handle when used.

In one aspect, the nonionic surfactant is at least selected from the group consisting of alkoxylate surfactants, fatty acid ester surfactants, amide surfactants, alcohol surfactants, ethylenediamine surfactants and silicone surfactants It may include any one.

In one aspect, the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether (alkyl C ₈ ~ C ₁₈ ), polyoxy Ethylene polyoxypropylene copolymer, polyoxyethylene stearyl amine, sorbitan fatty acid ester, glycerin fatty acid ester, primary alcohol ethoxylate, phenol ethoxylate, nonylphenol ethoxylate, octylphenol ethoxylate, lauryl Alcohol ethoxylate, oleyl alcohol ethoxylate, fatty acid ester-based, amide-based, natural alcohol-based, ethylenediamine-based, at least one selected from the group consisting of secondary alcohol ethoxylate-based and alkyl glucoside May be

In one aspect, the nonionic surfactant may be 0.3 wt% to 3 wt% of the surface treatment composition. When the nonionic surfactant is less than 0.3% by weight of the surface treatment composition, abrasive particles and metal impurities cannot be effectively cleaned, and even if it exceeds 3% by weight, no further effect is obtained and economical cost It costs more than this.

As an example of the present invention, the anionic surfactant is easy to remove residual particles and impurities, and improves cleaning and defects of hydrophilic films such as silicon nitride films and silicon oxide films.

In one side, the anionic surfactant, sulfonic acid group (-SO ₃ H), carboxyl group (-COOH), phosphonic group (-PO ₃ H ₂ ), phosphinic group (-HPO ₂ H), sulfate ester (-O · SO ₃ H), fatty acid ions (-COO-), sulfate ions (-OSO _3- ) and sulfite ions (-SO _3- ) may include at least one selected from the group consisting of.

In one aspect, the anionic surfactant, alkylbenzenesulfonic acid, alkylsulfonic acid, alkanesulfonic acid, alkylarylsulfonic acid, polystyrenesulfonic acid, alpha-olefinsulfonic acid, dodecylbenzenesulfonic acid, alkyl sulfate, alkyl ether sulfate ( alkyl ether sulfate), alkyl sulfate ester, alkyl ether sulfate ester, ether carboxylic acid, polyoxyethylene lauryl ether acetic acid, polyoxyethylene tridecyl ether carboxylic acid, polyoxyethylene lauryl ether phosphoric acid, polyoxyethylene arylphenyl ether phosphoric acid It may be one containing at least one selected from the group consisting of amines and salts thereof.

In one aspect, the anionic surfactant may be from 0.01% to 3% by weight of the surface treatment composition. When the anionic surfactant is less than 0.01% by weight of the surface treatment composition, the decontamination ability of the semiconductor film may not be exerted, and even if it exceeds 3% by weight, further effects are not obtained and cost is also economical. It costs more.

In the present invention, by using the nonionic surfactant and the anionic surfactant at the same time, chemical mechanical polishing (CMP) followed by surface treatment with the surface treatment composition of the present invention changes the wafer surface properties for semiconductor devices in a subsequent cleaning process. Surface defects can be significantly lowered. Preferably, defects on the surface of the silicon nitride film and the polysilicon film can be lowered.

In one aspect, the content ratio of the nonionic surfactant / anionic surfactant may be 0.75 or less, preferably 0.5 or less. When the content ratio of the nonionic surfactant and the anionic surfactant exceeds 0.75, it is not only possible to obtain a sufficient effect to change the wafer surface for semiconductor devices, but also to increase the possibility that the surfactant is adsorbed on the wafer surface. You can.

In the present invention, a change in the contact angle can be controlled through a combination of a nonionic surfactant and an anionic surfactant. When using nonionic surfactants and anionic surfactants at the same time, the contact angle can be increased, but the surface treatment process after chemical mechanical polishing (CMP) aims to remove contaminants such as abrasive particles, organic substances and impurities remaining on the surface after polishing. Therefore, it is preferable not to affect the surface other than the surface treatment action. Therefore, even in the contact angle after the surface treatment, in order to prevent the surfactant from remaining in an excessive amount on the surface while the desired level of surface treatment is performed based on the contact angle before the surface treatment, the contact angle is different when the content ratio of the nonionic surfactant / anionic surfactant exceeds 0.75. It is preferable to use it at 0.75 or less, as it becomes large.

In one aspect, the amount of change in the contact angle of water with respect to the wafer surface for semiconductor devices surface-treated with the surface treatment composition and the contact angle of water with respect to the wafer surface for semiconductor devices before surface treatment may be 2 ° to 7 °. The increase in the contact angle after the surface treatment with the surface treatment composition means that the hydrophobic material has a hydrophobic property because the surface is attached. This change facilitates cleaning in subsequent cleaning processes and reduces wafer defects. As an example of the present invention, a wafer for a semiconductor device is supported on the surface treatment composition for a few seconds, then washed with ultrapure water, and water is dropped on the surface of the wafer for a semiconductor device in a dry state with nitrogen gas to measure a contact angle. If there is no change in the contact angle, the surface modification does not appear, and if it is too high, the surfactant may remain on the surface and cause defects, so it is important to realize the characteristics by controlling the optimal contact angle.

In one aspect, the pH adjusting agent, monoethanolamine, methylethanolamine, ethylethanolamine, diethanolamine, triethanolamine and N-amino-N-propanol, methylamine, dimethylamine, trimethylamine, ethylamine, di Ethylamine, triethylamine, ethylenediamine, monoethanolamine, N- (β-aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine anhydride, piperazine Hexahydrate, 1- (2-aminoethyl) piperazine and N-methylpiperazine, ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonium hydrogencarbonate, ammonium carbonate, potassium hydrogencarbonate, carbonic acid Potassium, sodium hydrogen carbonate, sodium carbonate, ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, hydrogen carbonate Cerium, it may be one containing at least one selected from the group consisting of potassium carbonate, sodium bicarbonate and sodium carbonate.

In one side, the pH of the surface treatment composition may be 2 to 7. When included in the pH range, when the chemically mechanically polished (CMP) wafer is treated with the surface treatment composition, excellent cleaning effect and low defects may be provided in a subsequent cleaning process. In addition, contaminants such as abrasive particles, organic substances, and impurities remaining after polishing of the semiconductor wafer can be sufficiently removed.

In one aspect, the surface treatment composition includes a solvent, and the solvent may include water and / or an organic solvent. Water in the surface treatment composition serves to dissolve or disperse other components in the surface treatment composition. It is preferable that water does not contain impurities which inhibit the action of other components as much as possible. Specifically, ion-exchanged water in which impurities are removed through a filter after removing impurity ions using an ion-exchange resin, or pure water, ultrapure water, deionized water or distilled water is preferable.

In one aspect, the surface treatment composition is a silicon nitride film, silicon oxide film, polysilicon film and at least one film selected from the group consisting of a silicon device for changing the wafer surface properties for semiconductor devices including defects, residues and contaminants It may be to remove.

On one side, after surface treatment with the surface treatment composition, when hydrofluoric acid cleaning and SC1 cleaning were carried out in a subsequent cleaning process, defects in the silicon nitride film were only carried out by hydrofluoric acid cleaning and SC1 cleaning without surface treatment. The defect reduction rate is 80% or more based on the defect at the time, and the defect reduction rate for the polysilicon film may be 75% or more based on the defect when only hydrofluoric acid cleaning and SC1 cleaning are performed without surface treatment. . The defect reduction rate is an index indicating the level of defect reduction when a surface treatment is performed on a defect when the surface treatment is not performed.

When the surface treatment composition of the present invention is used, the defect improvement effect is excellent not only for the silicon nitride film but also for the polysilicon film .

The surface treatment composition of the present invention may be a surface treatment by directly contacting the wafer for semiconductor devices.

On one side, the residue is CMP abrasive slurry-derived particles, chemicals present in the CMP abrasive slurry, reaction by-products of the CMP abrasive slurry, carbon rich particles, abrasive pad particles, brush unloading particles, equipment material of the constituent particles, It may include a material selected from the group consisting of metals, metal oxides and combinations thereof.

The surface treatment composition according to an embodiment of the present invention includes a nonionic surfactant and an anionic surfactant to chemically buff the surface of a wafer for semiconductor devices after chemical mechanical polishing to change the surface properties, and nonionic surfactant And anionic surfactants to improve wettability on the wafer surface to facilitate cleaning and defect removal in subsequent cleaning processes.

In another aspect of the present invention, using the surface treatment composition according to an aspect of the present invention, to provide a surface treatment method, the semiconductor device wafer after the chemical mechanical polishing of the wafer for semiconductor devices.

The surface treatment composition of the present invention can be used in the same apparatus and conditions as those used in surface treatment of ordinary wafers. It can be used in the CMP module, not the cleaning module in the surface treatment device. When the wafer is surface-treated by the surface treatment method of the present invention, the temperature at the time of use of the surface treatment composition is not particularly limited, but may be 5 to 60 ° C.

The surface treatment of the wafer by the surface treatment method of the present invention may be a surface treatment for changing the surface properties of the polished wafer, or may be included in a cleaning process for cleaning the polished wafer. The surface treatment time generally proceeds for several seconds to several minutes, and may be performed within 1 second to 10 minutes.

Subsequent cleaning may be further included after the surface treatment of the present invention. Subsequent cleaning can be applied to all cleaning methods that are generally performed, for example, hydrofluoric acid cleaning, SC1 cleaning, cleaning using other commercially available cleaning solutions, or the like. When the surface treatment of the present invention is carried out, even if the cleaning process conventionally used is simplified, the same or more effects can be exhibited. For example, when hydrofluoric acid cleaning and SC1 cleaning are applied together after surface treatment, the same effect can be expected even if only the SC1 cleaning is performed without performing hydrofluoric acid cleaning.

By the surface treatment method of the present invention, it is possible to easily remove defects in a subsequent cleaning process by changing the surface characteristics of the wafer for semiconductor devices after chemical mechanical polishing.

Hereinafter, the present invention will be described in detail with reference to the following examples and comparative examples. However, the technical spirit of the present invention is not limited or limited thereby.

[Test Example 1]

2% by weight of citric acid as chelating agent, ethylene oxide as nonionic surfactant, sulfonate content ratio (nonionic surfactant / anionic surfactant) as anionic surfactant is 0.05, and monoethanolamine ( MEA) was added to prepare a surface treatment composition having a pH of 3.

[Test Example 2]

In Test Example 1, a surface treatment composition was prepared in the same manner as in Test Example 1, except that the content ratio of sulfonate (nonionic surfactant / anionic surfactant) as ethylene oxide and anionic surfactant was 0.25. .

[Test Example 3]

In Test Example 1, a surface treatment composition was prepared in the same manner as in Test Example 1, except that the content ratio of sulfonate (nonionic surfactant / anionic surfactant) was 0.50 as ethylene oxide and anionic surfactant. .

[Test Example 4]

In Test Example 1, a surface treatment composition was prepared in the same manner as in Test Example 1, except that the content ratio of sulfonate (nonionic surfactant / anionic surfactant) was 0.75 as ethylene oxide and anionic surfactant. .

Contact angle measurement

The silicon nitride film wafer was immersed in the surface treatment composition for 30 seconds, washed with DIW, and dried with N ₂ to prepare a wafer for measurement. Then, DIW (2 µl) was dropped on the wafer surface to measure the contact angle. KRUSS DSA100 was used as the contact angle measurement equipment.

Table 1 shows the contact angle change by measuring the contact angle of the silicon nitride film wafer with the surface treatment composition of Test Examples 1 to 4 of the present invention, and FIG. 1 shows the surface treatment composition of Test Examples 1 to 4 of the present invention. It shows a photograph of the measurement of the contact angle of water on the surface of the silicon nitride film.

As can be seen in Table 1, it can be seen that as the ratio of the nonionic surfactant and the anionic surfactant increases from 0.05 to 0.75, the amount of change in the contact angle increases. Since the amount of change in the contact angle was judged to be a modified degree, it was confirmed that the residue was effectively removed from the silicon nitride film wafer surface.

Wafer Defect Measurement

CMP polishing was performed for 15 seconds at a pressure of 1 psi and 200 ml of a polysilicon wafer and a silicon nitride film wafer using a colloidal silica slurry (pH 2) having a diameter of 130 nm. The polished polysilicon wafer and silicon nitride film wafer were subjected to the surface treatment for 12 seconds at 0.5 psi pressure and 500 ml conditions using the surface treatment compositions according to Examples 1 to 10 and Comparative Examples 1 to 8 below. Did.

Thereafter, after cleaning for 10 seconds using 1% hydrofluoric acid, and cleaning for 30 seconds using an SC1 solution, defects were measured for each of the polysilicon wafer and the silicon nitride film wafer using a defect measurement equipment (KLA-Tencor). Confirmed.

Here, ammonia and hydrogen peroxide mixture (APM) (NH ₄ OH: H ₂ O ₂ : H ₂ O) was used as the SC1 solution.

[Defect evaluation criteria]

No separate surface treatment was performed, followed by cleaning for 10 seconds using 1% hydrofluoric acid, and cleaning for 30 seconds using an SC1 solution, followed by defects measured for each of the polysilicon wafer and the silicon nitride film wafer. . The defects of the silicon nitride film wafer (≥53 nm) were 3,800 levels, and the defects of the polysilicon wafer (≥80 nm) were 80 levels.

Defects when the surface treatment was performed using the surface treatment compositions of Examples 1 to 10 and Comparative Examples 1 to 8 were compared with the defect reduction ratio (%) compared to defects without surface treatment as shown in Table 2. ).

[Comparative Example 1]

A composition having a pH of 3 was prepared by adding 2% by weight of citric acid as a chelating agent, 1.0% by weight of polyoxyethylene stearyl amine as a nonionic surfactant, and monoethanolamine as a pH adjusting agent.

[Comparative Example 2]

In Comparative Example 1, a composition was prepared in the same manner as in Comparative Example 1, except that lauryl alcohol ethoxylate was added as a nonionic surfactant.

[Comparative Example 3]

A composition having a pH of 8 was prepared by adding 2% by weight of citric acid as a chelating agent, 1.0% by weight of a polyoxyethylene polyoxypropylene copolymer as a nonionic surfactant, and monoethanolamine as a pH adjusting agent.

[Comparative Example 4]

In Comparative Example 3, a composition was prepared in the same manner as in Comparative Example 3, except that monoethanol amine was added so that the pH was 10.

[Comparative Example 5]

A composition having a pH of 3 was prepared by adding 2% by weight of citric acid as a chelating agent, 1.0% by weight of polystyrene sulfonate as an anionic surfactant, and monoethanolamine as a pH adjusting agent.

[Comparative Example 6]

2 wt% citric acid as a chelating agent, 1.0 wt% alcohol ethoxylate and alkyl glucoside as a nonionic surfactant, 1.0 wt% alkylaryl sulfonate as anionic surfactant, and monoethanolamine as a pH adjusting agent to give a pH of 8 The composition was prepared.

[Comparative Example 7]

A composition having a pH of 8 by adding 2% by weight of citric acid as a chelating agent, 1% by weight of lauryl alcohol ethoxylate as a nonionic surfactant, 1.0% by weight of alpha-olefinsulfonic acid as anionic surfactant, and monoethanolamine as a pH adjusting agent Was prepared.

[Comparative Example 8]

In Comparative Example 7, a composition was prepared in the same manner as in Comparative Example 7, except that monoethanol amine was added so that the pH was 10.

[Example 1]

2% by weight of citric acid as a chelating agent, 1.0% by weight of lauryl alcohol ethoxylate as a nonionic surfactant, 0.5% by weight of ammonium polyoxyethylene alkylaryl sulfonate as anionic surfactant, and pH by adding monoethanolamine as a pH adjusting agent A surface treatment composition of 3 was prepared.

[Example 2]

In Example 1, a surface treatment composition was prepared in the same manner as in Example 1, except that 1.0 wt% of dodecylbenzenesulfonic acid was added as an anionic surfactant.

[Example 3]

In Example 1, a surface treatment composition was prepared in the same manner as in Example 1, except that 1.5% by weight of lauryl alcohol ethoxylate as a nonionic surfactant and 2.0% by weight of polystyrene sulfonate as anionic surfactant were added. .

[Example 4]

In Example 1, the surface treatment composition was the same as in Example 1, except that 1.5% by weight of lauryl alcohol ethoxylate as a nonionic surfactant and 2.0% by weight of polyoxyethylene aryl ether sulfate as anionic surfactant were added. Was prepared.

[Example 5]

In Example 1, the surface treatment composition was the same as in Example 1, except that 1.0% by weight of polyoxyethylene polyoxypropylene block copolymer as nonionic surfactant and 1.0% by weight of polystyrene sulfonate as anionic surfactant were added. Was prepared.

[Example 6]

In Example 1, a surface treatment composition was prepared in the same manner as in Example 1, except that 1.0% by weight of polyoxyethylene stearyl amine as a nonionic surfactant and 1.0% by weight of alkyl aryl sulfonate as anionic surfactant were added. Did.

[Example 7]

In Example 1, the surface treatment was the same as in Example 1, except that 0.5% by weight of a polyoxyethylene polyoxypropylene copolymer as a nonionic surfactant and 2.0% by weight of a linear alkylbenzene sulfonate as anionic surfactant were added. The composition was prepared.

[Example 8]

In Example 1, a surface treatment composition was prepared in the same manner as in Example 1, except that 1.0% by weight of polyoxyethylene polyoxypropylene alkyl ether as a nonionic surfactant and 2.0% by weight of alkylsulfate as anionic surfactant were added. Did.

[Example 9]

In Example 8, a surface treatment composition was prepared in the same manner as in Example 8, except that 2.0% by weight of an alkyl ether sulfate was added as an anionic surfactant.

[Example 10]

In Example 8, a surface treatment composition was prepared in the same manner as in Example 8, except that sodium alkane sulfonate was added as an anionic surfactant.

Table 2 below summarizes the specific compositions and concentrations of the surface treatment compositions of Examples 1 to 10 and the compositions of Comparative Examples 1 to 8. Table 3 below shows the types of nonionic surfactants and anionic surfactants numerically listed in Table 2.

Looking at Table 2, Comparative Examples 1 to 4, which are compositions containing only a nonionic surfactant among surfactants, showed that defects of the silicon nitride film and defect levels of the polysilicon film were not good. In addition, in Comparative Example 5, a composition containing only an anionic surfactant, the defect level of the polysilicon film was improved, but it was confirmed that the defect level of the silicon nitride film was not good. Comparative Examples 6 to 8 include both a nonionic surfactant and an anionic surfactant, but the pH is adjusted to be basic, and the defect level is deteriorated compared to Examples 1 to 10 in which the pH is acidic. Can be confirmed.

The acidic surface treatment compositions of Examples 1 to 10 have excellent defect reduction rates in each of the silicon nitride film and the polysilicon film without variation, and in particular, the defect reduction rate in the silicon nitride film is 75% or more while the defect reduction rate in the polysilicon film is more than 75%. It was found to be 80% or more.

In the present invention, surface treatment of a CMP wafer is changed by surface treatment using a surface treatment composition containing a chelating agent, a nonionic surfactant, and an anionic surfactant, thereby eliminating defects in a subsequent cleaning process. It can be seen that it is easy.

As described above, although the embodiments have been described with limited drawings, those skilled in the art can apply various technical modifications and variations based on the above. For example, even if the described techniques are performed in a different order than the described method, and / or the described components are combined or combined in a different form from the described method, or replaced or replaced by another component or equivalent Appropriate results can be achieved.

Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (19)

Chelating agents; Nonionic surfactants; Anionic surfactants; And pH adjusting agent; The surface treatment composition comprising a. According to claim 1, The chelating agent, an organic acid, a compound containing a phosphate group, or those containing both, surface treatment composition. According to claim 2, The organic acid may be a linear saturated carboxylic acid having one carboxyl group; Saturated aliphatic dicarboxylic acid; Unsaturated aliphatic dicarboxylic acid; Aromatic dicarboxylic acids; And carboxylic acid having three or more carboxyl groups; at least any one selected from the group consisting of, The linear saturated carboxylic acid having one carboxyl group, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid ), Heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, undecylenic acid, lauric acid, tridecyl acid ( tridecylic acid), myristic acid (myristic acid), pentadecanoic acid (pentadecanoic acid) and at least one selected from the group consisting of palmitic acid. The saturated aliphatic dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, It includes at least one selected from the group consisting of suberic acid, azelaic acid and sebacic acid, The unsaturated aliphatic dicarboxylic acid is at least one selected from the group consisting of maleic acid, fumaric acid, glutaconic acid, traumatic acid and muconic acid. Including, The aromatic dicarboxylic acid, at least one selected from the group consisting of phthalic acid (phthalic acid), isophthalic acid (isophthalic acid) and terephthalic acid (terephthalic acid), The carboxylic acid having three or more carboxyl groups is citric acid, isocitric acid, aconic acid, carballylic acid, tribasic acid and melitic acid ( mellitic acid), surface treatment composition comprising at least one selected from the group consisting of. According to claim 2, The compound containing the phosphate group, at least one selected from the group consisting of phosphate ion (3 base), hydrogen phosphate ion (2 base), dihydrogen phosphate (1 base) and trihydrogen phosphate (acid) It comprises, a surface treatment composition. According to claim 2, The compound containing the phosphate group is ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropylidene-1,1'-diphosphonic acid, 1-hydroxybutylidene-1,1'-diphosphonic acid, ethylaminobis (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), 2-phosphono-butane-1,2,4-tri Carboxylic acid (2-phosphono-butane-1,2,4-tricarboxylic acid, PBTC), nitrilotris (methylenephosphonic acid) (NTPO), ethylenediaminebis (methylenephosphonic acid) (EDDPO), 1,3- Propylenediaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) (EDTPO), ethylenediaminetetra (ethylenephosphonic acid), 1,3-propylenediaminetetra (methylenephosphonic acid) (PDTMP), 1,2- Diaminopropanetetra (methylenephosphonic acid), 1,6-hexamethylenediaminetetra (methylenephosphonic acid), hexenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) ) (DEPPO), diethylenetriaminepentakis (methylphosphonic acid), N, N, N ', N'-ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (ethylenephosphonic acid), triethylenetetra Surface treatment composition comprising at least one selected from the group consisting of minhexa (methylenephosphonic acid) and triethylenetetraminehexa (ethylenephosphonic acid). According to claim 1, The chelating agent is 0.5 to 5% by weight of the surface treatment composition, the surface treatment composition. According to claim 1, The nonionic surfactant includes at least one selected from the group consisting of alkoxylate surfactants, fatty acid ester surfactants, amide surfactants, alcohol surfactants, ethylenediamine surfactants, and silicone surfactants. The surface treatment composition. According to claim 1, The nonionic surfactant is polyoxyalkylene alkyl ether, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether (alkyl C8 to C18), polyoxyethylene polyoxypropylene copolymer, Polyoxyethylene stearyl amine, sorbitan fatty acid ester, glycerin fatty acid ester, primary alcohol ethoxylate, phenol ethoxylate, nonylphenol ethoxylate, octylphenol ethoxylate, lauryl alcohol ethoxylate, oleyl A surface treatment composition comprising at least one selected from the group consisting of alcohol ethoxylate, fatty acid ester, amide, natural alcohol, ethylenediamine, secondary alcohol ethoxylate, and alkyl glucoside. According to claim 1, The nonionic surfactant is 0.3 to 3% by weight of the surface treatment composition, the surface treatment composition. According to claim 1, The anionic surfactant, sulfonic acid group (-SO ₃ H), carboxyl group (-COOH), phosphonic group (-PO ₃ H ₂ ), phosphinic group (-HPO ₂ H), sulfate ester (-OSO ₃ H), a fatty acid ion (-COO-), sulfate ion (-OSO _3- ) and sulfite ion (-SO _3- ) at least any one selected from the group consisting of, surface treatment composition. According to claim 1, The anionic surfactant, alkylbenzenesulfonic acid, alkylsulfonic acid, alkanesulfonic acid, alkylarylsulfonic acid, polystyrenesulfonic acid, alpha-olefinsulfonic acid, dodecylbenzenesulfonic acid, alkyl sulfate, alkyl ether sulfate, In the group consisting of alkyl sulfate esters, alkyl ether sulfate esters, polyoxyethylene lauryl ether acetic acid, polyoxyethylene tridecyl ether carboxylic acid, polyoxyethylene lauryl ether phosphoric acid, polyoxyethylene arylphenyl ether phosphate and salts thereof It comprises at least any one selected, surface treatment composition. According to claim 1, The anionic surfactant, 0.01 to 3% by weight of the surface treatment composition, the surface treatment composition. According to claim 1, The content ratio of the nonionic surfactant / anionic surfactant is 0.75 or less, surface treatment composition. According to claim 1, The pH adjusting agent is monoethanolamine, methylethanolamine, ethylethanolamine, diethanolamine, triethanolamine and N-amino-N-propanol, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethyl Amines, ethylenediamine, monoethanolamine, N- (β-aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine anhydride, piperazine hexahydrate, 1- (2-aminoethyl) piperazine and N-methylpiperazine, ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonium hydrogencarbonate, ammonium carbonate, potassium hydrogencarbonate, potassium carbonate, sodium hydrogencarbonate , Sodium carbonate, ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, potassium hydrogen carbonate, potassium carbonate, It is to include at least one selected from the group consisting of sodium carbonate and sodium oxyhydrogen, the surface treatment composition. According to claim 1, The pH of the surface treatment composition is 2 to 7, the surface treatment composition. According to claim 1, The surface treatment composition is to remove defects, residues and contaminants on the wafer surface for a semiconductor device including at least one film selected from the group consisting of a silicon nitride film, a silicon oxide film, a polysilicon film, and a silicon film. Composition. The method of claim 16, The amount of change in the contact angle of water on the surface of the wafer for semiconductor devices surface-treated with the surface treatment composition and the contact angle of water on the surface of the wafer for semiconductor devices before surface treatment is 2 ° to 7 °. The method of claim 16, When surface-treated with the surface treatment composition, the defect reduction rate for the silicon nitride film is 80% or more, and the defect reduction rate for the polysilicon film is 75% or more. A surface treatment method comprising using the surface treatment composition according to claim 1 to surface-treat a semiconductor device wafer after chemical mechanical polishing of the semiconductor device wafer.

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