KR102518902B1 - Cleaning solution composition for post cmp process - Google Patents

Abstract

The present invention relates to a post-CMP cleaning liquid composition, and the post-CMP cleaning liquid composition according to an embodiment of the present invention may include a surfactant containing a nonionic functional group and an anionic functional group and an aqueous solvent. Surface defects of a hydrophobic film of a semiconductor wafer can be effectively removed by using the post-CMP cleaning liquid composition according to the present invention.

Description

Cleaning liquid composition after CMP {CLEANING SOLUTION COMPOSITION FOR POST CMP PROCESS}

The present invention relates to a post-CMP cleaning liquid composition and a post-CMP cleaning process using the same.

A chemical mechanical polishing (CMP) process is performed by putting a slurry containing abrasive particles on a substrate and using a polishing pad mounted on a polishing device. At this time, the abrasive particles mechanically polish the surface by receiving pressure from the polishing device, and the chemical components included in the slurry composition chemically react with the surface of the substrate to chemically remove the surface portion of the substrate.

Although the surface of the substrate is flattened through the physicochemical polishing using the slurry composition, the substrate stained with the slurry and abrasive particles that have undergone the chemical mechanical process becomes contaminated.

Therefore, as a final step of the chemical mechanical process, a process of removing particles such as slurry from the substrate while supplying pure water to the polishing plate, or immersing the substrate after the chemical mechanical process in a wetting bath, It is necessary to perform a process of removing particles such as slurry.

The above background art is possessed or acquired by the inventor in the process of deriving the disclosure of the present application, and cannot necessarily be said to be known art disclosed to the general public prior to the present application.

In order to solve the above problems, the present invention is to provide a cleaning liquid composition after CMP and a cleaning method after CMP polishing of a semiconductor wafer using the same.

Specifically, the post-CMP cleaning liquid composition according to the present invention is for removing slurry, abrasive particles and other contaminants, and provides a cleaning liquid composition containing an anionic functional group and a nonionic functional group to reduce the number of surface defects of a substrate to be effectively removed.

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

The post-CMP cleaning liquid composition according to one aspect of the present invention includes a surfactant containing a nonionic functional group and an anionic functional group; And an aqueous solvent; may include.

According to one embodiment of the present invention, the surfactant may be a compound represented by Formula 1 below.

[Formula 1]

(At this time, R ₁ is a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₁ to C ₃₀ alkylene group, a substituted or unsubstituted C ₂ to C 30 alkenyl group, a substituted or unsubstituted C 1 to C ₃₀ alkenyl group, Unsubstituted C ₃ to C ₃₀ cycloalkyl group, substituted or unsubstituted C ₃ to C ₃₀ cycloalkylene group, substituted or unsubstituted C ₅ to C ₃₀ cycloalkenyl group, substituted or unsubstituted C ₆ to C 30 cycloalkenyl group A C ₅₀ aryl group, a substituted or unsubstituted C ₆ to C ₅₀ arylene group, a substituted or unsubstituted C ₂ to C ₅₀ heteroaryl group, and a substituted or unsubstituted C ₂ to C ₅₀ heteroarylene group any one selected from

R ₂ is SO ₃ R' (where R' is any one selected from the group consisting of hydrogen, NH ₄ , an alkali metal element, and a C ₁ to C ₆ alkanol amine residue), a phosphate group, and phospho Any one anionic group selected from phosphonate,

A is a substituted or unsubstituted C ₂ to C ₄ alkylene group,

n is an integer from 1 to 200).

According to one embodiment of the present invention, the surfactant may be a compound represented by Formula 2 below.

[Formula 2]

(At this time, R ₃ is a substituted or unsubstituted C ₁ to C ₃₀ alkyl group,

R ₄ is any one selected from a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₁ to C ₃₀ alkylene group, or an allyl group;

R ₅ is SO ₃ R' (where R' is any one selected from the group consisting of hydrogen, NH ₄ , an alkali metal element, and a C ₁ to C ₆ alkanol amine residue), a phosphate group, and phospho Any one anionic group selected from phosphonate,

A is a substituted or unsubstituted C ₂ to C ₄ alkylene group,

n is an integer from 1 to 200).

According to one embodiment of the present invention, the surfactant may be 0.001% to 10% by weight.

According to one embodiment of the present invention, a second surfactant; may further include.

According to one embodiment of the present invention, the second surfactant contains C ₂ to C ₄ ethylene oxide, amine oxide, or both in its molecular structure, and the second surfactant contains 0.001% by weight to 5% by weight.

According to one embodiment of the present invention, a hydrophilic agent; may be further included, and the hydrophilic agent may be 0.005% by weight to 10% by weight.

According to one embodiment of the present invention, the hydrophilic agent includes at least one selected from the group consisting of dimethyl succinate, dimethyl glutarate, and dimethyl adipate. can

According to one embodiment of the present invention, a pH adjusting agent comprising a carboxylic acid-based organic acid; further comprising, wherein the carboxylic acid-based organic acid as the pH adjusting agent is citric acid, lactic acid, or gluconic acid , maleic acid, ascorbic acid, iminoacetic acid, oxalic acid, pyrogallic acid, formic acid, acetic acid, propionic acid ( propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid acid), undecylenic acid, lauric acid, tridecylic acid, myristic acid, pentadecanoic acid and palmitic acid. It may include at least one selected from the group consisting of.

According to one embodiment of the present invention, the antifoaming agent further includes, and the antifoaming agent may include an alcohol-based compound, a polyalkylene-based compound, or both.

According to one embodiment of the present invention, the antifoaming agent may be included in 1% by weight or less.

According to one embodiment of the present invention, the cleaning liquid composition after CMP reacts with a contaminant on the surface of at least one hydrophobic film selected from the group consisting of an amorphous carbon layer (ACL) film, a silicon film, and a polysilicon film to form micelles ( micelle) may be formed.

According to one embodiment of the present invention, the cleaning liquid composition after CMP may have a contact angle of 70° or less with respect to a hydrophobic film substrate.

According to one embodiment of the present invention, the cleaning liquid composition after CMP may have a surface tension of 50 mN/m or less.

The present invention can provide a post-CMP cleaning liquid composition and a cleaning method after CMP polishing of a semiconductor wafer using the same

Specifically, the post-CMP cleaning liquid composition according to the present invention can effectively remove the number of surface defects by providing a cleaning liquid composition containing an anionic functional group and a nonionic functional group.

1 is a graph showing the measurement of the surface tension of a cleaning liquid composition over time after cleaning according to Experimental Example 2.

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

Terms used in the examples are used only for descriptive purposes and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

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 overlapping descriptions thereof will be omitted. In describing the embodiment, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the embodiment, the detailed description will be omitted.

In addition, in describing the components of the embodiment, terms such as first, second, A, B, (a), and (b) may be used. These terms are only used to distinguish the component from other components, and the nature, sequence, or order of the corresponding component is not limited by the term. When an element is described as being “connected”, “coupled” or “connected” to another element, the element may be directly connected or connected to the other element, but there may be another element between the elements. It should be understood that may be "connected", "coupled" or "connected".

Components included in one embodiment and components including common functions will be described using the same names in other embodiments. Unless stated to the contrary, descriptions described in one embodiment may be applied to other embodiments, and detailed descriptions will be omitted to the extent of overlap.

The present invention relates to a cleaning liquid composition after CMP, in the CMP process In order to remove various contaminations that may occur on the wafer surface, it can be used in the process of cleaning or surface treating the CMP-completed wafer after the CMP process.

The post-CMP cleaning liquid composition according to an embodiment of the present invention may be applied on a semiconductor wafer to perform a subsequent cleaning process on the surface of the wafer polished by a polishing device. In addition, surface contamination can be removed by the chemical action of the cleaning liquid composition after CMP.

A cleaning liquid composition after CMP according to an embodiment of the present invention includes a surfactant containing a nonionic functional group and an anionic functional group; And an aqueous solvent; may include.

According to one embodiment, the surfactant may include a nonionic functional group, and the nonionic functional group may have a C ₂ to C ₄ polyalkylene oxide structural unit. Nonionic functional groups can increase the hydrophilicity of the surface of the wafer.

According to one embodiment, the surfactant may form a micellar structure by surrounding contamination by including a nonionic functional group, and may improve wettability of a wafer surface.

According to one embodiment, the micelle structure formed by surrounding the contamination with a surfactant isolates the contamination from the semiconductor and can be easily dissolved in water.

According to one embodiment, the surfactant may include an anionic functional group, and the anionic functional group may be selected from a sulfonic acid group, a sulfonate group, a phosphate group, and a phosphonate group.

According to one embodiment, the surfactant contains an anionic functional group, thereby adsorbing contaminants remaining after the CMP process (eg, abrasive particles, residual polishing slurry, by-products, residues, etc. generated during polishing) and the wafer surface to generate negative charges. and a repulsive force is formed between the surface of the contaminant and the surface of the wafer to remove the contaminant, Re-adsorption of contaminants to the surface can be prevented.

According to one embodiment, the cleaning liquid composition after CMP may be an aqueous solution containing a surfactant.

According to one embodiment, the surfactant may be a compound represented by Formula 1 or Formula 2 below.

[Formula 1]

At this time, R ₁ is a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₁ to C ₃₀ alkylene group, a substituted or unsubstituted C ₂ to C 30 alkenyl group, or a substituted or unsubstituted C 1 to C ₃₀ alkenyl group. Cyclic C ₃ to C ₃₀ cycloalkyl group, substituted or unsubstituted C ₃ to C ₃₀ cycloalkylene group, substituted or unsubstituted C ₅ to C ₃₀ cycloalkenyl group, substituted or unsubstituted C ₆ to C ₅₀ aryl group, a substituted or unsubstituted C ₆ to C ₅₀ arylene group, a substituted or unsubstituted C ₂ to C ₅₀ heteroaryl group, and a substituted or unsubstituted C ₂ to C ₅₀ heteroarylene group which one is selected,

R ₂ is SO ₃ R' (where R' is any one selected from the group consisting of hydrogen, NH ₄ , an alkali metal element, and a C ₁ to C ₆ alkanol amine residue), a phosphate group, and phospho Any one anionic group selected from phosphonate,

A is a substituted or unsubstituted C ₂ to C ₄ alkylene group,

n is an integer from 1 to 200;

[Formula 2]

At this time, R ₃ is a substituted or unsubstituted C ₁ to C ₃₀ alkyl group,

R ₄ is any one selected from a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₁ to C ₃₀ alkylene group, or an allyl group;

R ₅ is SO ₃ R' (where R' is any one selected from the group consisting of hydrogen, NH ₄ , an alkali metal element, and a C ₁ to C ₆ alkanol amine residue), a phosphate group, and phospho Any one anionic group selected from phosphonate,

A is a substituted or unsubstituted C ₂ to C ₄ alkylene group,

n is an integer from 1 to 200;

According to one embodiment of the present invention, the surfactant may be 0.001% to 10% by weight.

According to one embodiment, if the surfactant is contained less than 0.001% by weight, contamination and contact on the surface of the wafer are reduced, and the surfactant cannot sufficiently cover the contamination, so that the desired cleaning effect cannot be obtained, and the content of the surfactant is 10% by weight. If it is higher than this, a lot of bubbles are generated, and the cleaning effect does not increase, which is inefficient in terms of economics, and there is a disadvantage in that organic defects are generated by remaining on the surface.

According to one embodiment of the present invention, the aqueous solvent may be water. Water includes purified water, deionized water, reverse osmosis water, and the like, and may include at least one of purified water, deionized water, and reverse osmosis water, but is not limited thereto.

According to one embodiment of the present invention, the cleaning liquid composition after CMP may further include a second surfactant.

According to one embodiment, the second surfactant may be adsorbed on the surface of the semiconductor wafer to increase wettability. In addition, the second surfactant may form a micelle structure by combining with contamination on the surface of the wafer.

According to one embodiment of the present invention, the second surfactant may include C ₂ to C ₄ polyalkylene oxide, amine oxide, or both in its molecular structure.

According to one embodiment, the second surfactant may include any one selected from polyoxyethylene alkyl ether, polyoxyethylene aryl ether, alkyl amine oxide, and aryl amine oxide.

According to one embodiment, the alkyl group may be C ₁ to C ₂₀ , and the aryl group may be C ₆ to C ₂₀ .

According to one embodiment, the second surfactant is decamine oxide, decylamine oxide, octyldimethylamine oxide, lauryldimethylamine oxide, polyoxyethylene Polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether oleyl ether) may include at least one selected from the group consisting of.

According to one embodiment, the second surfactant may be included in an amount of 0.001% to 5% by weight, and when the content of the second surfactant is lower than 0.001% by weight, contamination and contact of the wafer surface are reduced to prevent contamination. The activator may not be sufficiently surrounded, and if the content of the second surfactant is higher than 5% by weight, a lot of bubbles are generated, and the cleaning effect is no longer increased, which is inefficient in terms of economy, and remains on the surface, resulting in organic defects There is a downside to

According to one embodiment of the present invention, the cleaning liquid composition after CMP, It further includes a hydrophilic agent, and the hydrophilic agent may be 0.005% by weight to 10% by weight.

According to one embodiment, the hydrophilic agent may include one or more alkyl groups; It may include; and an atom with high electronegativity selected from N, O, or F. Since it contains an alkyl group, it can increase the van der Waals force to enhance the adsorption force with the hydrophobic membrane, and contains atoms (N, O, F, etc.) with high electronegativity, enabling hydrogen bonding with water, making the wafer The surface can be made hydrophilic.

According to one embodiment, the hydrophilic agent is dialkyl malate, dialkyl succinate, dialkyl glutarate, dialkyl adipate, dialkyl pi It may include at least one selected from the group consisting of dialkyl pimelate, dialkyl suberate, carboxamide, polyethylene imine, and urethane-modified polymer.

According to one embodiment, the alkyl group included in the hydrophilic agent may include at least one selected from the group consisting of a methyl group, an ethyl group, and a propyl group.

According to one embodiment, the content of the hydrophilic agent may be 0.005% by weight to 10% by weight. If the content of the hydrophilic agent is less than 0.005% by weight, the degree of hydrophilization of the surface may decrease and the cleaning effect may decrease, and if the content exceeds 10% by weight, solubility in water may decrease.

According to one embodiment of the present invention, the hydrophilic agent is, preferably, at least one selected from the group consisting of dimethyl succinate, dimethyl glutarate and dimethyl adipate It may contain.

According to one embodiment of the present invention, a pH adjusting agent containing a carboxylic acid-based organic acid; further comprising, wherein the pH adjusting agent containing a carboxylic acid-based organic acid is citric acid, lactic acid, gluconic acid acid), maleic acid, ascorbic acid, iminoacetic acid, oxalic acid, pyrogallic acid, 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 ) It may include at least one selected from the group consisting of.

According to one embodiment, the cleaning liquid composition after CMP may have different cleaning performance depending on the pH, and the pH of the cleaning liquid composition after CMP may be preferably 5 to 7.

The pH adjusting agent may be used in an amount necessary to adjust the pH of the cleaning liquid composition to a desired value after CMP.

According to one embodiment of the present invention, the antifoaming agent further includes, and the antifoaming agent may be non-silicone-based, and may include an alcohol-based compound, a polyalkylene-based compound, or both.

According to one embodiment, the cleaning performance of the cleaning composition after CMP may be improved as bubbles are removed, and accordingly, the polishing performance of the cleaning composition according to an embodiment of the present invention may be improved by adding an antifoaming agent.

According to one embodiment, the antifoaming agent is tert -butyl alcohol ( tert -Butyl alcohol), tert -amyl alcohol ( tert -Amyl alcohol), 3-methyl-3-pentanol (3-Methyl-3-pentanol), enanthic alcohol, capryl alcohol, pelargonic alcohol, capric alcohol, undecyl alcohol, lauryl alcohol, polyoxy It may include at least one selected from the group consisting of ethylene lauryl amine ester (Polyoxyethylene lauryl amine ether) and polyalkylene.

According to one embodiment of the present invention, the antifoaming agent may be included in 1% by weight or less.

According to one embodiment, when the content of the antifoaming agent exceeds 1% by weight, solubility may decrease and layer separation may occur.

According to one embodiment, the cleaning liquid composition after CMP may modify or clean the surface of at least one hydrophobic film selected from the group consisting of an amorphous carbon layer (ACL) film, a silicon film, and a polysilicon film.

According to one embodiment of the present invention, the cleaning liquid composition after CMP may have a contact angle of 70° or less with respect to a hydrophobic film substrate.

According to one embodiment, examples of the hydrophobic film substrate may include at least one selected from the group consisting of an ACL substrate, a silicon substrate, and a polysilicon substrate.

According to one embodiment of the present invention, the cleaning liquid composition after CMP may have a surface tension of 50 mN/m or less.

According to one embodiment, when the surface tension of the composition is strong, the wetting strength of the surfactant with the film to be cleaned may decrease. In addition, since contaminants present on the surface of the film to be cleaned cannot easily penetrate the interface between the film and the film to be cleaned, cleaning performance may be deteriorated.

According to one embodiment, the surface tension of the cleaning liquid composition after CMP may be preferably 30 mN/m or less, and more preferably 25 mN/m or less.

A method for cleaning a semiconductor wafer after CMP according to an embodiment of the present invention is a semiconductor wafer including a hydrophobic film whose surface is polished using a polishing slurry, and polished using a cleaning liquid composition after CMP. Cleaning or surface treatment of the semiconductor wafer; and the removal rate of defects according to Equation 1 below on the surface of the semiconductor wafer including the hydrophobic film subjected to the cleaning step may be 95% or more.

[Equation 1]

(However, a contaminant having a diameter of 80 nm or more is called a defect.)

According to one embodiment, the cleaning liquid composition after CMP may be a cleaning liquid composition after CMP according to an embodiment of the present invention.

According to one embodiment, the defect in Equation 1 has a size of 80 nm or more, and the contamination having a size of less than that is very small, so it is a problem in a subsequent process after the CMP process (eg, a post-cleaning process) may not occur.

According to one embodiment, the CMP process may be to polish a wafer under a predetermined pressure for a predetermined time using a silica slurry having abrasive particles, and after polishing, the surface of the wafer may be cleaned using a cleaning solution composition after CMP. Through the above process, defects of 80 nm or more can be significantly removed, and the defect removal rate may be significantly increased compared to the case where deionized water is used as the cleaning liquid composition.

According to an embodiment, the number of defects when a post-CMP cleaning process is performed using the post-CMP cleaning composition according to an embodiment of the present invention compared to the number of defects removed by using deionized water as a cleaning solution is 95% or more. It may be a sharp decline. In other words, when cleaning is performed using the post-CMP cleaning liquid composition according to an embodiment of the present invention, defects that remain even after cleaning is performed with deionized water, not when cleaning is not performed, reduce defects by 95% or more. it may be

According to one embodiment, the removal rate of defects of 80 nm or more according to Equation 1 on the surface of the hydrophobic coating film subjected to the cleaning or surface treatment step may be preferably 97% or more.

According to one embodiment of the present invention, the cleaning or surface treatment step; Thereafter, the step of subsequent cleaning the semiconductor wafer; further comprising, wherein the subsequent cleaning step is performed by deionized water brush cleaning, SC1 brush cleaning, NH ₄ OH brush cleaning, IPA cleaning or O ₃ cleaning. can

Hereinafter, the present invention will be described in more detail by examples and comparative examples.

However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited to the following examples.

Example 1

A cleaning liquid composition having a pH of 5 was prepared including 5% by weight of a compound having the structure of Formula 3 below as a surfactant containing a nonionic functional group and an anionic functional group and water.

[Formula 3]

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

Example 2

A cleaning liquid composition having a pH of 5 containing 5% by weight of a surfactant containing a nonionic functional group and an anionic functional group of Example 1, 1% by weight of dimethyl succinate, and water was prepared.

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

Example 3

8% by weight of isooctyl alcohol polyoxyethylene ether phosphate, 3% by weight of polyoxyethylene alkyl ether having an alkyl group of C ₁ to C ₂₀ , 1% by weight of dimethyl succinate and water A cleaning liquid composition of pH 5 was prepared.

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

Example 4

A cleaning solution of pH 7 containing 5% by weight of a surfactant containing a nonionic functional group and an anionic functional group of Example 1, 1% by weight of decamine oxide, 1% by weight of dimethyl succinate and water A composition was prepared.

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

Comparative Example 1

A cleaning solution composition containing deionized water was prepared.

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

Comparative Example 2

A cleaning liquid composition having a pH of 3 containing 5% by weight of C ₃ to C ₁₂ polyoxyethylene alkyl ether, 2% by weight of polyacrylate and water was prepared.

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

Comparative Example 3

A cleaning liquid composition having a pH of 5 containing 2% by weight of polyacrylate and water was prepared.

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

Comparative Example 4

A cleaning liquid composition having a pH of 5 containing 5% by weight of C ₃ to C ₁₂ polyoxyethylene alkyl ether, 2% by weight of polyacrylate and water was prepared.

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

Comparative Example 5

A cleaning liquid composition having a pH of 5 containing 5% by weight of C ₃ to C ₁₂ polyoxyethylene alkyl ether and water was prepared.

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

Comparative Example 6

A cleaning liquid composition having a pH of 5 containing 3% by weight of lauryl betaine and water was prepared.

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

Comparative Example 7

A cleaning liquid composition of pH 2 containing 5% by weight of a surfactant containing a nonionic functional group and an anionic functional group of Example 1 and water was prepared.

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

Comparative Example 8

A cleaning liquid composition having a pH of 3 containing 5% by weight of a surfactant containing a nonionic functional group and an anionic functional group of Example 1 and water was prepared.

The wafer was polished at 2 psi pressure for 60 seconds using a silica slurry with 80 nm diameter abrasive particles. Thereafter, the surface of the wafer was treated for 12 seconds using the cleaning liquid composition on a platen. Thereafter, a subsequent cleaning process was performed using a brush.

The components and pH of the cleaning composition according to Examples 1 to 4 and Comparative Examples 1 to 8 are shown in Table 1 below.

division Surfactants content
(wt%) Second surfactant content
(wt%) hydrophilic agent content
(wt%) pH Example 1 Compound represented by Formula 3 5 - - 5 Example 2 Compound represented by Formula 3 5 Dimethyl succinate One 5 Example 3 Isooctyl alcohol polyoxyethylene ether phosphate 8 Polyoxyethylene alkyl ether 3 Dimethyl succinate One 5 Example 4 Compound represented by Formula 3 5 Decamine oxide One Dimethyl succinate One 7 Comparative Example 1 DIW - Comparative Example 2 Polyoxyethylene alkyl ether 5 Polyacrylate 2 3 Comparative Example 3 - Polyacrylate 2 5 Comparative Example 4 Polyoxyethylene alkyl ether 5 Polyacrylate 2 5 Comparative Example 5 Polyoxyethylene alkyl ether 5 - - 5 Comparative Example 6 Lauryl betaine 3 - - 5 Comparative Example 7 Compound represented by Formula 3 5 - - 2 Comparative Example 8 Compound represented by Formula 3 5 - - 3

Experimental Example 1

After polishing a silicon wafer with a size of 2 cm × 2 cm with a polishing pad using a silica slurry, surface treatment with the cleaning solution composition according to Examples 2, 3, and 4 and Comparative Example 1, followed by nitrogen drying (N ₂ drying ), and then the contact angle on the silicon wafer was measured.

According to Experimental Example 1, the contact angle of the CMP cleaning liquid composition was measured and shown in Table 2 below.

division Contact angle (°) Example 2 63.20 Example 3 62.97 Example 4 59.70 Comparative Example 1 83.01

Referring to Table 2, it can be seen that the contact angle is 70° or less in the case of the cleaning liquid composition including a surfactant including a nonionic functional group and an anionic functional group. On the other hand, when using the cleaning liquid composition of Comparative Example 1 containing only deionized water, it can be confirmed that the contact angle with respect to the silicon substrate reaches 83.01°.

Experimental Example 2

After performing stirring for 30 seconds with respect to the cleaning composition according to Examples 2, 3, 4 and Comparative Example 1, the surface tension was measured until an equilibrium state was reached.

1 is a graph showing the measurement of the dynamic surface tension of a cleaning liquid composition over time after cleaning according to Experimental Example 2;

Referring to FIG. 1, unlike the cleaning composition of Comparative Example 1, it can be seen that the cleaning composition of Examples 2 to 4 in which a surfactant containing an anionic functional group and a cationic functional group is added has significantly lower surface tension.

Experimental Example 3

After surface treatment of the wafers using the cleaning composition according to Examples 1 to 4 and Comparative Examples 1 to 8, the number of defects was confirmed using a defect measurement equipment manufactured by KLA-tencor. At this time, the defect removal rate was calculated according to Equation 1 below, and after CMP using deionized water, cleaning was performed using the remaining cleaning solution composition based on the number of defects (when the cleaning solution composition according to Comparative Example 1 was used) according to the cleaning process. The defect removal rate when the process was performed was measured.

[Equation 1]

The number of defects according to Experimental Example 3 and the defect removal rate calculated using Equation 1 are shown in Table 3 below.

division number of defects Defect removal rate (%) Example 1 3,175 97.5 Example 2 3,803 97.0 Example 3 1,972 98.4 Example 4 1,172 99.1 Comparative Example 1 126,085 0.0 Comparative Example 2 120,456 4.5 Comparative Example 3 109,191 13.4 Comparative Example 4 121,564 3.6 Comparative Example 5 92,701 26.5 Comparative Example 6 25,974 79.4 Comparative Example 7 19,957 84.2 Comparative Example 8 8,735 93.1

Referring to Table 3, it can be seen that, compared to Comparative Examples, a defect removal rate of 95% or more can be achieved when the cleaning liquid compositions of Examples are used.

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, the described techniques may be performed in an order different from the method described, and/or the components of the described system, structure, device, circuit, etc. may be combined or combined in a different form than the method described, or other components may be used. Or even if it is replaced or substituted by equivalents, appropriate results can be achieved.

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

Claims (14)

Surfactant containing a nonionic functional group and an anionic functional group; and
Including; aqueous solvent;
The surfactant is a compound represented by Formula 1 or Formula 2 below,
Post-CMP cleaning solution composition:
[Formula 1]

(At this time, R ₁ is a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₁ to C ₃₀ alkylene group, a substituted or unsubstituted C ₂ to C 30 alkenyl group, a substituted or unsubstituted C 1 to C ₃₀ alkenyl group, Unsubstituted C ₃ to C ₃₀ cycloalkyl group, substituted or unsubstituted C ₃ to C ₃₀ cycloalkylene group, substituted or unsubstituted C ₅ to C ₃₀ cycloalkenyl group, substituted or unsubstituted C ₆ to C 30 cycloalkenyl group A C ₅₀ aryl group, a substituted or unsubstituted C ₆ to C ₅₀ arylene group, a substituted or unsubstituted C ₂ to C ₅₀ heteroaryl group, and a substituted or unsubstituted C ₂ to C ₅₀ heteroarylene group any one selected from
R ₂ is any one anionic group selected from a phosphate group and a phosphonate group;
A is a substituted or unsubstituted C ₂ to C ₄ alkylene group,
n is an integer from 1 to 200),
[Formula 2]

(At this time, R ₃ is a substituted or unsubstituted C ₁ to C ₃₀ alkyl group,
R ₄ is any one selected from a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₁ to C ₃₀ alkylene group, or an allyl group;
R ₅ is SO ₃ R' (where R' is any one selected from the group consisting of hydrogen, NH ₄ , an alkali metal element, and a C ₁ to C ₆ alkanol amine residue), a phosphate group, and phospho Any one anionic group selected from phosphonate,
A is a substituted or unsubstituted C ₂ to C ₄ alkylene group,
n is an integer from 1 to 200).
delete delete According to claim 1,
The surfactant is, 0.001% by weight to 10% by weight,
Post-CMP cleaning liquid composition.
According to claim 1,
A second surfactant; further comprising,
Post-CMP cleaning liquid composition.
According to claim 5,
The second surfactant contains C ₂ to C ₄ ethylene oxide, amine oxide, or both in its molecular structure,
The second surfactant is 0.001% to 5% by weight,
Post-CMP cleaning liquid composition.
According to claim 1,
It further includes a hydrophilic agent;
The hydrophilic agent is 0.005% to 10% by weight,
Post-CMP cleaning liquid composition.
According to claim 7,
The hydrophilic agent includes at least one selected from the group consisting of dimethyl succinate, dimethyl glutarate, and dimethyl adipate,
Post-CMP cleaning liquid composition.
According to claim 1,
Further comprising a pH adjusting agent comprising a carboxylic acid-based organic acid,
The pH adjusting agent for the carboxylic acid-based organic acid is citric acid, lactic acid, gluconic acid, maleic acid, ascorbic acid, iminoacetic acid, Oxalic acid, pyrogallic acid, 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 acid), myristic acid, pentadecanoic acid, and palmitic acid, comprising at least one selected from the group consisting of
Post-CMP cleaning liquid composition.
According to claim 1,
Further comprising a defoamer;
The antifoaming agent comprises an alcohol-based compound, a polyalkylene-based compound, or both,
Post-CMP cleaning liquid composition.
According to claim 10,
The antifoaming agent is contained in 1% by weight or less,
Post-CMP cleaning liquid composition.
According to claim 1,
The cleaning liquid composition after CMP reacts with contaminants on the surface of at least one hydrophobic film selected from the group consisting of an amorphous carbon layer (ACL) film, a silicon film, and a polysilicon film to form micelles,
Post-CMP cleaning liquid composition.
According to claim 1,
The cleaning liquid composition after CMP has a contact angle of 70 ° or less with respect to a hydrophobic film substrate,
Post-CMP cleaning liquid composition.
According to claim 1,
The cleaning liquid composition after CMP has a surface tension of 50 mN / m or less,
Post-CMP cleaning liquid composition.

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