KR102352229B1 - CMP composition for polishing an organic layer and method of forming a semiconductor device using the composition - Google Patents

Abstract

The present invention provides a CMP slurry composition for polishing an organic film and a method for manufacturing a semiconductor device using the same. The CMP slurry composition contains 0.001 to 5% by weight of oxide abrasive particles; 0.1-5% by weight of an oxidizing agent; 0-5 wt% of abrasive control agent; 0 to 3% by weight of surfactant; 0 to 3% by weight of a pH adjuster; and deionized water in an amount of 79 to 99.889 wt%. The CMP slurry composition can polish an organic film containing no silicon with an excellent selectivity of 6:1 or more with respect to the oxide film.

Description

CMP slurry composition for polishing an organic film and a method for manufacturing a semiconductor device using the same

The present invention relates to a CMP slurry composition for polishing an organic film and a semiconductor manufacturing process using the same.

As semiconductor devices are highly integrated, formation of finer patterns and circuits having a multilayer structure are required. For this purpose, films of various materials having different etch selectivity characteristics are required. Among the films of various materials, the hydrocarbon-based organic film has good etch selectivity with respect to other silicon-containing films, and thus can be used as a mask film or a sacrificial film. In a semiconductor manufacturing process, it is required to remove the organic layer by performing a chemical mechanical polishing process. However, a CMP slurry composition that can be used to effectively chemically and mechanically polish an organic film has not yet been developed.

Accordingly, an object of the present invention is to provide a CMP slurry composition capable of effectively polishing an organic film.

Another problem to be solved by the present invention is to provide a semiconductor manufacturing process using the composition.

The CMP slurry composition according to the present invention for achieving the above object is used for polishing an organic film that does not contain silicon. The CMP slurry composition, the oxide abrasive particles in an amount of 0.001 to 5% by weight; 0.1-5% by weight of an oxidizing agent; 0-5 wt% of abrasive control agent; 0 to 3% by weight of surfactant; 0 to 3% by weight of a pH adjuster; and deionized water in an amount of 79 to 99.889 wt%.

The abrasive particles may be at least one selected from _{silica (SiO 2} ), ceria (CeO ₂ ), and alumina (Al ₂ O _{3 ).}

The particle size of the abrasive particles may be 30 ~ 120nm.

The oxidizing agent is hydrogen peroxide, superoxide, dioxygenyl, ozone, ozonide, peroxide, fluorine, chlorine, chlorite (Chlorite), Chlorate, Perchlorate, Halogen Compounds, Nitric acid, Nitrate, Hypochlorite, Hypohalite, Chromium Trioxide ( Chromium trioxide, Pyridinium chlorochromate, Chromate, Dichromate, Chromium Compound, Potassium permanganate, Permanganate, Sodium perborate ( Sodium perborate), nitrous oxide (Nitrous Oxide), 2,2'-dipyridisulfide (2,2'-Dipyridisulfide), lead dioxide (PbO ₂ ), manganese dioxide (MnO ₂ ), copper oxide (CuO), iron chloride (FeCl) ₃ ), perchloric acid (HClO ₄ ), iron nitrate (Fe(NO) ₃ ), sulfate and potassium thiosulfate (Potassium persulfate, K ₂ S ₂ O ₈ ) At least selected from the group comprising can be one

The polishing control agent is organic acid, inorganic acid, nitric acid, nitrate (Nitrate), sulfuric acid (Sulfuric acid), peroxydisulfuric acid (Peroxydisulfuric acid), peroxymonosulfuric acid (Peroxymonosulfuric acid), sulfonic acid ( Sulfonic acid, Acetic acid, Citric acid, Formic acid, Gluconic acid, Lactic acid, Oxalic acid, Tartaric acid, Carboxylic acid (Carboxylic acid), Chloric acid, Chlorous acid, Hypochlorous acid, Perchloric acid, Halogen oxoacid, Ascorbic acid, Vinyl group It may be at least one selected from the group consisting of acetic acid (vinylogous carboxylic acid), amino acid, histidine, glycine, arginine, hydrochloric acid, hydrofluoric acid, and phosphoric acid.

The surfactant may be anionic or nonionic. Specifically, the surfactant is a lauryl myristyl alcohol series, a methyl-oxirane polymer series having a hydrophile lipophile balance (HLB) value of 12 or more, ethylenediamine, ethoxylation selected from ethoxylated and propoxylated alcohol series, 2-methyloxirane, oxirane series, polyethylene glycol, or polysorbate series There may be at least one.

In addition, the surfactant is benzalkonium chloride, alkyl benzene sulfonate (Alkyl Benzene Sulfonate), pemerol chloride (Phemerol chloride), ammonium lauryl sulfate (ammonium lauryl sulfate), sodium lauryl ether sulfate ( sodium lauryl ether sulfate, sodium myreth sulfate, dioctyl sodium sulfosuccinate, perfluorooctanesulfonate, perfluorobutanesulfonate, linear alkyl Benzene sulfonate, sodium stearate, sodium lauroyl sarcosinate, cetyl trimethylammonium bromide, cetyl trimethylammonium chloride ), perfluorononanoate, perfluorooctanoate, octenidine dihydrochloride, 5-bromo-5-nitro-1,3-dioxane (5 -Bromo-5-nitro-1,3-dioxane), dimethyldioctadecylammonium chloride, cetrimonium bromide, dioctadecyldimethylammonium bromide, octaethylene Glycol monododecyl ether (Octaethylene glycol monododecyl ether), glyceryl laurate, or polyol It may be at least one selected from ethoxylated tallow amine.

The pH adjusting agent is at least one acid selected from the group consisting of polyacrylic acid, carboxylic acid, nitric acid, sulfuric acid and sulfonic acid, or potassium hydroxide, sodium hydroxide, aqueous ammonia, tetramethylammonium hydride It may be at least one base selected from the group including tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide.

The composition may preferably have a pH of 2.0 to 5.0.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a first structure including a first recess region on a substrate; filling the first recess region by forming an organic layer that does not include silicon on the first structure; and exposing the upper surface of the first structure by performing a CMP process on the organic layer using the CMP slurry composition of claim 1 .

In an example, the first recess region may be a first hole exposing the substrate, and in the method, after performing a CMP process on the organic layer, an upper surface of the organic layer on the first structure forming a second structure including a second hole exposing the second structure; removing the organic layer through the second hole; forming an active pillar covering at least sidewalls of the first hole and the second hole; and forming a conductive line in a portion of the first structure and the second structure.

Each of the first structure and the second structure may have a structure in which a plurality of insulating films and sacrificial films are alternately stacked, and forming a conductive line in a portion of the first structure and the second structure includes: selectively removing the sacrificial layers; and forming the conductive line in a region from which the sacrificial layers are removed.

In another example, the structure may include an etch target layer disposed on the substrate, a plurality of first mask patterns disposed on the etch target layer in the form of parallel lines, and sidewalls and upper portions of the first mask patterns A second mask layer may be included to conformally cover the surface, and the step of exposing the upper surface of the first structure may expose the upper surface of the second mask layer.

Specifically, the interval between the first mask patterns may be about three times the thickness of the second mask layer, and the organic layer may be disposed between the first mask patterns.

The method may further include removing the second mask layer exposed by performing an anisotropic etching process and forming a second mask pattern under the organic layer.

An oxide layer is disposed on the upper end of the first structure, and the CMP slurry composition may polish the organic layer at a selectivity ratio of 6:1 or more with respect to the oxide layer.

The CMP slurry composition according to an embodiment of the present invention can polish an organic film not containing silicon with an excellent selectivity ratio of 6:1 or more with respect to the oxide film. In addition, when the polishing process is performed using the present CMP slurry composition, the etching selectivity of the organic layer to the oxide layer may be variously realized in the range of about 6:1 to 430:1. The CMP composition may be applied by selecting an appropriate composition according to the structure of the semiconductor device to be manufactured. In addition, the CMP slurry composition does not cause peeling or delamination of the structure. Accordingly, the semiconductor device can be manufactured without defects.

1, 2A, and 2B are cross-sectional views illustrating a process of manufacturing a semiconductor device according to an embodiment of the present invention.
3 to 10 are cross-sectional views illustrating a process of manufacturing a semiconductor device according to an embodiment of the present invention.
11 to 17 are cross-sectional views illustrating a process of manufacturing a semiconductor device according to another example of the present invention.
18 is a schematic block diagram illustrating an example of a memory system including a semiconductor device manufactured according to embodiments of the present invention.
19 is a schematic block diagram illustrating an example of a memory card including a semiconductor device manufactured according to embodiments of the present invention.
20 is a schematic block diagram illustrating an example of an information processing system in which a semiconductor device manufactured according to embodiments of the present invention is mounted.

Advantages and features of the present invention, and methods for achieving them, will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and only this embodiment serves to complete the disclosure of the present invention, and to obtain common knowledge in the technical field to which the present invention pertains. It is provided to fully inform the possessor of the scope of the invention, and the present invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout.

The terminology used herein is for the purpose of describing the embodiments and is not intended to limit the present invention. In this specification, the singular also includes the plural unless specifically stated otherwise in the phrase. As used herein, 'comprises' and/or 'comprising' means that a referenced component, step, operation and/or element is the presence of one or more other components, steps, operations and/or elements. or addition is not excluded. Also, in this specification, when a certain film is referred to as being on another film or substrate, it means that it may be directly formed on the other film or substrate, or a third film may be interposed therebetween.

Further, the embodiments described herein will be described with reference to cross-sectional and/or plan views, which are ideal illustrative views of the present invention. In the drawings, thicknesses of films and regions are exaggerated for effective description of technical content. Accordingly, the shape of the illustrative drawing may be modified due to manufacturing technology and/or tolerance. Accordingly, the embodiments of the present invention are not limited to the specific form shown, but also include changes in the form generated according to the manufacturing process. For example, the etched region shown at a right angle may be rounded or have a predetermined curvature. Accordingly, the regions illustrated in the drawings have a schematic nature, and the shapes of the illustrated regions in the drawings are intended to illustrate specific shapes of regions of the device and not to limit the scope of the invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The nonvolatile memory device according to the embodiments of the present invention has a structure of a 3D semiconductor device having a 3D structure.

1, 2A, and 2B are cross-sectional views illustrating a process of manufacturing a semiconductor device according to an embodiment of the present invention.

Referring to FIG. 1 , a structure 110 including a recessed region 115 is formed on a substrate 100 . At least an upper portion of the structure 110 may be formed of an oxide. An organic layer 120 is formed on the structure 110 . The organic layer 120 may also be referred to as a spin on carbon layer or a spin on hardmask layer. The organic layer 120 is an organic layer that does not include silicon. The process of forming the organic layer 120 may include spin coating and drying or baking. The organic layer 120 is formed to fill the recessed region 115 .

2A and 2B , at least a portion of the organic layer 120 on the structure 110 is removed by polishing the organic layer 120 through a polishing process. The polishing process may be chemical mechanical polishing (CMP). At this time, as shown in FIG. 2A , an organic layer pattern 120a having a predetermined thickness is formed on the structure 110 or the polishing process is continued to expose the upper surface of the structure 110 as shown in FIG. 2B and the recessed region An organic layer pattern 120b may remain in the 115 . At this time, the CMP slurry composition used in the CMP process contains 0.001 to 5 wt% of oxide abrasive particles; 0.1-5% by weight of an oxidizing agent; 0-5 wt% of abrasive control agent; 0 to 3% by weight of surfactant; 0 to 3% by weight of a pH adjuster; and deionized water in an amount of 79 to 99.889 wt%.

The abrasive particles may be at least one selected from _{silica (SiO 2} ), ceria (CeO ₂ ), and alumina (Al ₂ O _{3 ).} The abrasive particles may have a particle size of 10 to 100 nm, preferably 30 to 120 nm.

The oxidizing agent induces oxidation of the organic layer to secure a polishing rate. The oxidizing agent is a peroxide series such as hydrogen peroxide, superoxide, dioxygenyl, ozone and ozonide, fluorine or chlorine and Halogen compounds such as chlorite, chlorite and perchlorate, nitrate containing nitric acid, hypo containing household cleaner Chromium compounds such as Hypochlorite, Hypohalite, Chromium trioxide, Pyridinium chlorochromate, Chromate and Dichromate ) series, permanganate series such as potassium permanganate, lead dioxide (PbO ₂ ), manganese dioxide (MnO ₂ ), high oxidation number compounds of metals such as copper oxide (CuO) and iron chloride (FeCl _{3 );} Sulfate such as potassium thiosulfate (Potassium persulfate, K ₂ S ₂ O ₈ ), perchloric acid (HClO ₄ ), iron nitrate (Fe(NO) ₃ ), sodium perborate (Sodium perborate), nitrous oxide (Nitrous Oxide) and 2,2'-dipyridisulfide (2,2'-Dipyridisulfide) may be at least one selected from the group consisting of. Among the oxidizing agents, chlorite or chlorate is most preferred.

The polishing control agent may serve to break the carbon chain in the organic layer. The polishing control agent is preferably organic acid (Organic Acid) or inorganic acid (Inorganic acid). Specifically, the polishing control agent is a nitrate (Nitrate) series including nitric acid, sulfuric acid (Sulfuric acid), peroxydisulfuric acid (Peroxydisulfuric acid) and peroxymonosulfuric acid (Sulfonic acid) series, such as sulfonic acid (Peroxymonosulfuric acid) series, acetic acid Carboxylic acids such as Acetic acid, Citric acid, Formic acid, Gluconic acid, Lactic acid, Oxalic acid, and Tartaric acid ) series, halogen oxoacid series such as chloric acid, chlorous acid and hypochlorous acid, perchloric acid, 　 vinyl group such as ascorbic acid It may be at least one selected from the group consisting of carboxylic acids, amino acids such as histidine, glycine and arginine, and inorganic acids such as hydrochloric acid, hydrofluoric acid and phosphoric acid. As the polishing control agent, a carboxylic acid series may be most preferable.

The surfactant may serve to increase the polishing rate by improving wettability on the surface of the organic layer of the CMP slurry composition. The surfactant may be anionic or nonionic. Specifically, the surfactant is a lauryl myristyl alcohol series, a methyl-oxirane polymer series having a hydrophile lipophile balance (HLB) value of 12 or more, ethylenediamine, C1- 16 Ethoxylated and propoxylated alcohol series, 2-methyloxirane, oxirane series, polyethylene glycol, or polysorbate series It may be at least one selected from.

In addition, the surfactant is benzalkonium chloride, alkyl benzene sulfonate (Alkyl Benzene Sulfonate), pemerol chloride (Phemerol chloride), ammonium lauryl sulfate (ammonium lauryl sulfate), sodium lauryl ether sulfate ( sodium lauryl ether sulfate, sodium myreth sulfate, dioctyl sodium sulfosuccinate, perfluorooctanesulfonate, perfluorobutanesulfonate, linear alkyl Benzene sulfonate, sodium stearate, sodium lauroyl sarcosinate, cetyl trimethylammonium bromide, cetyl trimethylammonium chloride ), perfluorononanoate, perfluorooctanoate, octenidine dihydrochloride, 5-bromo-5-nitro-1,3-dioxane (5 -Bromo-5-nitro-1,3-dioxane), dimethyldioctadecylammonium chloride, cetrimonium bromide, dioctadecyldimethylammonium bromide, octaethylene Glycol monododecyl ether (Octaethylene glycol monododecyl ether), glyceryl laurate, or polyol It may be at least one selected from ethoxylated tallow amine.

The pH adjusting agent functions to adjust the pH of the CMP slurry composition. Since the polishing control agent also contains an acid, it can serve as a kind of pH control agent. The pH adjusting agent may be acidic or basic. Specifically, the pH adjusting agent is an acid such as polyacrylic acid, carboxylic acid, nitric acid, sulfuric acid and sulfonic acid, or potassium hydroxide, sodium hydroxide, aqueous ammonia, tetramethylammonium hydroxide ), tetraethylammonium hydroxide (Tetraethylammonium hydroxide), and tetrabutylammonium hydroxide (Tetrabutylammonium hydroxide) may be a base.

The composition may preferably have a pH of 2.0 to 5.0.

The organic layer can be effectively polished using such a CMP slurry composition.

Next, experimental examples of the CMP slurry composition of the present invention will be described.

<Experimental Example 1: Type of Oxidizing Agent>

Eight wafers were prepared, an organic film not containing silicon was formed on each of the four wafers, and a tetraethyoxysilane (TEOS) film, which is one of the silicon oxide films, was formed on each of the remaining four wafers. 1 wt% of silica as an abrasive and 98 wt% of deionized water are the same, but the oxidizing agent is changed to a peroxide-based, chlorate, nitrate-based and highly oxidized compound, respectively, but the content of the oxidizing agent CMP slurry compositions were prepared by using 1 wt% of each. At this time, as the peroxide-based oxidizing agent, hydrogen peroxide was used. _{Perchloric acid (HClO 4} ) was used as the chlorate-based oxidizing agent. As the nitrate-based oxidizing agent, iron nitrate (Fe(NO) ₃ ) was used. The high oxidation number compound refers to a high oxidation number compound of a metal, and includes lead dioxide (PbO ₂ ), manganese dioxide (MnO ₂ ), copper oxide (CuO), iron chloride (FeCl ₃ ), and the like. The oxidizing agent used as the high oxidation number compound in Experimental Example 1 was iron chloride (FeCl ₃ ). The average particle size of the silica was about 60 nm. And, after the CMP process was performed on the two types of wafers with the CMP slurry compositions, the polishing rate and selectivity were investigated and recorded in Table 1 below.

type of oxidizer Grinding rate (Å/min) Organic film/TEOS selectivity organic film TEOS One peroxide series 1250 115 10.9 2 chlorate series 1530 95 16.1 3 nitrate series 920 89 10.3 4 highly oxidized compounds 870 112 7.8

In Table 1, the chlorate series showed the best polishing rate and selectivity. However, it can be seen that other peroxide series or nitrate series also exhibit a high selectivity of 6:1 or more, and thus are suitable as the oxidizing agent for polishing an organic film of the present invention.

<Experimental Example 2: Abrasive particles and oxidizing agent content>

In this Experimental Example 2, the polishing characteristics according to the content of the chlorate-based oxidizing agent and silica used as abrasive particles, which showed the best characteristics in Experimental Example 1, will be investigated. First, 34 wafers were prepared, an organic film containing no silicon was formed on each of the 17 wafers, and a tetraethyoxysilane (TEOS) film, which is one of the silicon oxide film series, was formed on the remaining 17 wafers, respectively. Next, as shown in Table 2, in the CMP slurry composition, while changing the content of the chlorate-based oxidizing agent to 0.1 to 3.0% by weight and the content of silica abrasive particles to 0.01 to 1.0% by weight, the CMP process is performed for each wafer to be polished characteristics were found. In Experimental Example 2, perchloric acid (HClO ₄ ) was used as a chlorate-based oxidizing agent. The average particle size of the silica was about 60 nm.

Oxidizing agent content (wt%) Abrasive grain content (wt%) Grinding rate (Å/min) Organic film/TEOS selectivity organic film TEOS One 1.2 0.4 1650 45 36.7 2 1.0 0.4 1620 40 40.5 3 0.7 0.4 1510 42 35.9 4 0.5 0.4 1400 40 35.0 5 1.0 0.7 1630 89 18.3 6 1.0 0.5 1620 62 26.1 7 1.0 0.3 1590 42 37.8 8 0.3 1.0 1158 121 9.6 9 0.2 1.0 941 124 7.6 10 0.1 1.0 804 129 6.2 11 3 0.01 1987 5 397.4 12 3 0.05 2100 6 350 13 3 0.1 2230 28 79.6 14 3 0.2 2480 48 51.7 15 3 0.5 2670 77 34.7 16 One 0.05 1505 8 188.1 17 One 0.1 1600 31 51.6

From Table 2, it can be seen that when the content of the chlorate-based oxidizer is 3 wt% and the concentration of the silica abrasive particles is 0.01 wt%, the selectivity is the highest at 397.4. In addition, it can be seen that the selectivity is excellent as 6 or more in the remaining contents, so that it is suitable as the composition for polishing an organic film of the present invention.

<Experimental Example 3-1: Type of abrasive control agent>

In this Experimental Example 3-1, the type and content of the polishing control agent was changed in the CMP slurry composition maintaining 1.0% by weight of the chlorate-based oxidizing agent, which exhibited the best properties in Experimental Example 2, and 0.4% by weight of silica used as abrasive particles. and to investigate the abrasive properties accordingly. First, 18 wafers were prepared, an organic film containing no silicon was formed on each of the nine wafers, and a plasma-enhanced tetraethyoxysilane (PETEOS) film, which is one of the silicon oxide film series, was formed on each of the remaining nine wafers. Next, as shown in Table 3, by changing the carboxylic acid to 0.1 to 1.0% by weight as a polishing control agent or to sulfonic acid, amino acid, inorganic acid, or nitric acid instead of carboxylic acid, the CMP process is performed for each wafer to improve the polishing properties. I found out In Experimental Example 3-1, perchloric acid (HClO ₄ ) was used as the chlorate-based oxidizing agent. Formic acid was used as the carboxylic acid. Histidine was used as the amino acid. Hydrochloric acid was used as the inorganic acid. The average particle size of the silica was about 60 nm.

Type of abrasive modifier Abrasive control agent content (wt%) Grinding rate (Å/min) Organic film/PETEOS selectivity organic film PETEOS One carboxylic acid 0.5 2010 48 41.9 2 carboxylic acid 0.3 1990 42 47.4 3 carboxylic acid 0.1 1820 41 44.4 4 carboxylic acid 0.7 2580 45 57.3 5 carboxylic acid 1.0 3340 42 79.5 6 sulfonic acid 0.3 1800 47 38.3 7 amino acid 0.3 1710 45 38.0 8 inorganic acid 0.3 1690 43 39.3 9 nitric acid 0.3 1720 43 40.0

In Table 3, a CMP slurry composition comprising 1.0 wt% of a chlorate-based oxidizing agent and 0.4 wt% of silica used as abrasive particles, 1.0 wt% of carboxylic acid as a polishing control agent, and the remainder being deionized water This showed the best selectivity value of 79.5. In addition, it can be seen that the selectivity ratio of 38 or more is very excellent in the remaining experimental results, and thus it is suitable as the composition for polishing an organic film of the present invention.

<Experimental Example 3-2: Type of abrasive control agent>

In this Experimental Example 3-2, the type and content of the polishing control agent was changed in the CMP slurry composition maintaining 1.0 wt% of a chlorate-based oxidizing agent and 0.2 wt% of silica used as abrasive particles, and the polishing properties were investigated accordingly. . First, six wafers were prepared, an organic film containing no silicon was formed on each of the three wafers, and a plasma-enhanced tetraethyoxysilane (PETEOS) film, which is one of the silicon oxide films, was formed on the remaining three wafers, respectively. Next, as shown in Table 4, the CMP process was performed for each wafer while changing the carboxylic acid to 0.7 to 1.3 wt% as a polishing control agent to investigate the polishing characteristics. In Experimental Example 3-1, perchloric acid (HClO ₄ ) was used as the chlorate-based oxidizing agent. Formic acid was used as the carboxylic acid. The average particle size of the silica was about 60 nm.

Type of abrasive modifier Abrasive control agent content (wt%) Grinding rate (Å/min) Organic film/PETEOS selectivity organic film PETEOS One carboxylic acid 0.7 2600 24 108.3 2 carboxylic acid 1.0 3500 22 159.1 3 carboxylic acid 1.3 4410 21 210.0

In Table 4, when 1.0 wt% of the chlorate-based oxidizing agent and 0.2 wt% of silica used as abrasive particles are included, and the carboxylic acid is adjusted to 0.7 to 1.3 wt% as an abrasive control agent, the selectivity is very high to 108.3 to 210.0 Could know.

<Experimental Example 4: Types of Surfactants>

In Experimental Example 4, cationic, anionic and non-ionic surfactants were added to a CMP slurry composition containing 1.0 wt% of a chlorate-based oxidizing agent, 0.4 wt% of silica abrasive particles, and 0.3 wt% of carboxylic acid. After adding it by changing it into an ionic system, we will examine the polishing properties accordingly. To this end, six wafers were prepared, an organic film containing no silicon was formed on each of the three wafers, and a plasma-enhanced tetraethyoxysilane (PETEOS) film, which is one of the silicon oxide film series, was formed on each of the remaining three wafers. Next, CMP slurry compositions were prepared in which the surfactant was changed as described above. At this time, the amount of each type of surfactant added was 0.5% by weight based on the total weight of the composition. As the cationic surfactant, benzalkonium chloride was used. As the anionic surfactant, Alkyl Benzene Sulfonate was used. As the nonionic surfactant, polyethylene glycol was used. _{Perchloric acid (HClO 4} ) was used as the chlorate-based oxidizing agent. Formic acid was used as the carboxylic acid. The average particle size of the silica was about 60 nm. Then, a CMP process was performed on each wafer using the CMP slurry compositions, and the polishing properties were investigated and recorded in Table 5.

Surfactant type Surfactant content (wt%) Organic film/PETEOS selectivity One cationic 0.5 56 2 anionic 0.5 73 3 nonionic 0.5 102

From Table 5, it can be seen that the best selectivity value of 102 is shown when a nonionic surfactant is added. Regardless of the type of surfactant, a selectivity ratio of 56 or more was obtained only by adding the surfactant. After nonionic surfactants, anionic surfactants were excellent. In addition, it was found that when the surfactant was added, the peeling phenomenon of the surface of the organic film was significantly improved compared to the case where the surfactant was not added. This can be presumed to be because the wettability of the CMP composition of the present invention was increased on the surface of the organic film by the surfactant, and the polishing effect was uniformly applied over the entire surface.

<Experimental Example 5-1>

In Experimental Example 5-1, it was investigated how the polishing properties change according to the pH of the CMP composition of the present invention. First, 0.5 wt% of silica particles having a particle size of about 60 nm were added, and 1.0 wt% of perchloric acid as a chlorate-based oxidizer was added. At this time, the pH became about 2.1. Eight samples of this same composition were prepared. The pH was adjusted by adding a pH adjuster to 7 of 8 samples. At this time, the added pH adjusting agent was added in an amount of 3 wt% or less of the total composition. In two of the seven samples, nitric acid was added little by little as a pH adjuster to lower the pH to lower the pH to 1.8 and 2.0, respectively. To the remaining 5 samples among the 7 samples, potassium hydroxide (KOH) was added little by little as a pH adjuster to raise the pH to 2.2 to 3.0, respectively. Then, using each sample, a CMP process was performed on an organic film that does not contain silicon and a TEOS film, which is a kind of oxide film, respectively, and the polishing characteristics were investigated and recorded in Table 6.

Experiment number composition pH Grinding rate (Å/min) Organic film/TEOS selectivity abrasive grain stability organic film TEOS One 1.8 1403 55 25.5 bad 2 2.0 1470 57 25.8 bad 3 2.1 1580 60 26.3 good 4 2.2 1620 62 26.1 good 5 2.4 1610 60 26.8 good 6 2.6 1520 61 24.9 good 7 2.8 1480 59 25.1 bad 8 3.0 1420 58 24.5 bad

In Table 6, it was shown to have an excellent selectivity of 24.5 or more regardless of the pH of the composition. However, 'bad' in particle stability in Table 6 means that problems such as sinking or color change of silica particles in the composition occur. As such, when the abrasive grain stability is not good, uniform surface polishing properties were not exhibited in the polishing process. From Table 6, it can be seen that when the CMP composition of Experimental Example 5-1 contains silica particles in an amount of 0.5% by weight and perchloric acid as a chlorate-based oxidizer in an amount of 1.0% by weight, the preferred pH is about 2.1 to 2.6.

<Experimental Example 5-2>

In Experimental Example 5-2, it was investigated how the abrasive grain stability was changed according to the pH of the CMP composition of the present invention. First, silica particles having a particle size of about 60 nm were added at 0.5 wt%, and potassium thiosulfate (K ₂ S ₂ O ₈ ) as a sulfate-based oxidizer was added at 0.3 wt%. At this time, the pH became about 4.2. Three composition samples having this composition were made. The pH was adjusted by adding a pH adjusting agent to two of the three samples. At this time, the added pH adjusting agent was added in an amount of 3 wt% or less of the total composition. Sulfuric acid was added little by little as a pH adjuster to one of the three samples to lower the pH, and the abrasive grain stability was visually observed while measuring the pH. At this time, when the pH was lowered to less than 3.5, the abrasive grain stability deteriorated. Potassium hydroxide (KOH) was added little by little as a pH adjuster to the other one of the three samples to increase the pH, and the abrasive grain stability was visually observed while measuring the pH. At this time, when the pH exceeded 5.0, the abrasive grain stability deteriorated. Thus, when the CMP composition of Experimental Example 5-2 contains silica particles in an amount of 0.5% by weight and potassium thiosulfate (Potassium persulfate, K ₂ S ₂ O ₈ ) in an amount of 0.3% by weight, the preferred pH is about 3.5 to It can be seen that 5.0.

<Experimental Example 5-3>

In Experimental Example 5-2, it was investigated how the abrasive grain stability was changed according to the pH of the CMP composition of the present invention. First, ceria particles having a particle size of about 60 nm were added in an amount of 0.5 wt%, and iron nitrate (Fe(NO) ₃ ) as a nitrate-based oxidizer was added in an amount of 0.3 wt%. At this time, the pH became about 2.1. Three composition samples having this composition were made. The pH was adjusted by adding a pH adjusting agent to two of the three samples. At this time, the added pH adjusting agent was added in an amount of 3 wt% or less of the total composition. To one of the three samples, nitric acid was added little by little as a pH adjuster to lower the pH, and the abrasive grain stability was visually observed while measuring the pH. At this time, when the pH was lowered to less than 2.0, the abrasive grain stability deteriorated. Potassium hydroxide (KOH) was added little by little as a pH adjuster to the other one of the three samples to increase the pH, and the abrasive grain stability was visually observed while measuring the pH. At this time, when the pH exceeded 2.8, the abrasive grain stability deteriorated. Accordingly, it can be seen that when the CMP composition of Experimental Example 5-3 contains ceria particles in an amount of 0.5% by weight and iron nitrate (Fe(NO) ₃ ) in an amount of 0.3% by weight, the preferred pH is about 2.0 to 2.8.

<Experimental Example 6>

In Experimental Example 6, it was investigated how the polishing properties were changed according to the size of the silica abrasive particles of the present invention. Silica abrasive particles were added in an amount of 0.5 wt%, and perchloric acid as a chlorate-based oxidizer was added in an amount of 1.0 wt%. Then, four composition samples having silica abrasive particles each having a size of about 30 nm, 60 nm, 80 nm, and 120 nm were prepared. Using each sample, a CMP process was performed on an organic film that does not contain silicon and a TEOS film, which is a type of oxide film, respectively, and the polishing characteristics were investigated and recorded in Table 7.

Experiment number Silica particle size (nm) Grinding rate (Å/min) Organic film/TEOS selectivity organic film TEOS One 30 1550 50 31 2 60 1620 62 26.1 3 80 2100 88 23.9 4 120 2430 101 24.1

Referring to Table 7, it can be seen that when the silica particle size is 120 nm or less, the selectivity is 23.9 or more, which is good.

<Experimental Example 7>

In Experimental Example 7, ceria was used as the oxide abrasive particles of the present invention. And how the abrasive properties change according to the size of the ceria abrasive particles were investigated. Ceria abrasive particles were added in an amount of 0.05 wt% and iron nitrate as an oxidizing agent was added in an amount of 3.0 wt%. And three composition samples having a size of about 30 nm, 60 nm, and 80 nm of ceria abrasive particles, respectively, were prepared. Using each sample, a CMP process was performed on an organic film that does not contain silicon and a TEOS film, which is a type of oxide film, respectively, and the polishing characteristics were investigated and recorded in Table 7.

Experiment number Seria
Particle size (nm) Grinding rate (Å/min) Organic film/TEOS selectivity organic film TEOS One 30 1720 4 430 2 60 2100 6 350 3 80 2450 12 204

Referring to Table 8, it can be seen that when ceria is used as the oxide abrasive particles, the selectivity is very excellent in the range of 204 to 430. In addition, it can be seen that the selectivity increases as the ceria particle size decreases.

Through various experimental examples as described above, the etch selectivity of the organic layer to the oxide layer can be variously implemented in the range of about 6:1 to about 430:1. The CMP composition may be applied by selecting an appropriate composition according to the structure of the semiconductor device to be manufactured.

Next, a detailed manufacturing process of a semiconductor device to which the CMP composition of the present invention can be applied will be described.

3 to 10 are cross-sectional views illustrating a process of manufacturing a semiconductor device according to an embodiment of the present invention.

Referring to FIG. 3 , a first structure 10 is formed by alternately stacking first gate interlayer insulating layers 3 and first sacrificial layers 5 on a substrate 1 . The first sacrificial layers 5 may be formed of a material having an etch selectivity to the first gate interlayer insulating layers 3 . The first gate interlayer insulating layers 3 may be, for example, silicon oxide layers, and the first sacrificial layers 5 may be silicon nitride layers. The first sacrificial layers 5 and the first gate interlayer insulating layers 3 are sequentially etched to form a first hole 12 exposing the substrate 1 .

Referring to FIG. 4 , an organic layer 14 not containing silicon is formed on the first structure 10 to fill the first holes 12 .

Referring to FIG. 5 , a CMP process is performed on the organic layer 14 using the CMP composition to remove the organic layer 14 on the first structure 10 and the uppermost first gate interlayer insulating layer (3) is exposed. At this time, since the CMP composition has an excellent polishing selectivity for the oxide film and a high polishing rate for the organic film, the CMP process can be performed quickly without defects. Accordingly, the organic layer pattern 14a remains in the first hole 12 .

Referring to FIG. 6 , the second structure 20 is formed by alternately stacking second gate interlayer insulating layers 23 and second sacrificial layers 25 on the first structure 10 . The second sacrificial layers 25 may be the same as the first sacrificial layers 5 . The second gate interlayer insulating layers 23 may be the same as the first gate interlayer insulating layers 3 . The second sacrificial layers 25 and the second gate interlayer insulating layers 23 are sequentially etched to form a second hole 22 exposing the organic layer pattern 14a. In this case, the organic layer pattern 14a serves to protect the first hole 12 and the substrate 1 at the bottom thereof.

Although the structures 10 and 20 of two layers are formed in this example, the number of stacked structures of the structures may be three or more layers.

Referring to FIG. 7 , an ashing process using oxygen is performed to selectively remove the organic layer pattern 14a exposed through the second hole 22 . Accordingly, the substrate 1 may be exposed at the bottom of the first hole 12 .

Referring to FIG. 8 , a polysilicon film is conformally formed on the entire surface of the substrate 1 , a first buried insulating film is formed to fill the holes 12 and 22 , and then the holes 12 and 22 are etched by planarization. ), the active pillars 27 covering the sidewalls and the bottom thereof and the first buried insulating film pattern 29 filling them are formed. In addition, an ion implantation process may be performed to form the common drain region 31 on the upper end of the active pillar 27 .

Referring to FIG. 9 , the structures 20 and 10 spaced apart from the active pillar 27 are patterned to form a groove 32 exposing the substrate 1 . The sacrificial layers 5 and 25 are removed through the groove 32 . A gate insulating layer 34 is conformally formed in the region from which the sacrificial layers 5 and 25 have been removed, and a conductive layer is formed to form a conductive layer in the regions from which the sacrificial layers 5 and 25 are removed and the groove 32 . fill The gate insulating layer 34 may include a tunnel insulating layer, a charge trap layer, and a blocking insulating layer. The conductive layer may be polysilicon doped with impurities or a metal-containing layer. Then, the conductive layers in the groove 32 are removed again to expose the substrate 1 , and at the same time, the lower selection line LSL and the word lines WL0 to WL3 are disposed between the gate interlayer insulating layers 3 and 23 . and upper selection lines USL0 and USL1.

Referring to FIG. 10 , an ion implantation process is performed to form a common source line CSL under the groove 32 . After the groove 32 is filled with a second buried insulating layer, planarization etching is performed to leave a second buried insulating layer pattern 34 in the groove 32 . A plurality of bit lines BL in contact with the common drain region 31 but spaced apart from each other are formed on the uppermost second gate interlayer insulating layer 23 .

3 to 10 illustrate a process in which the CMP composition of the present invention is applied in the process of manufacturing a vertical NAND memory device.

11 to 17 are cross-sectional views illustrating a process of manufacturing a semiconductor device according to another embodiment of the present invention.

Referring to FIG. 11 , an etch target layer 53 is formed on a substrate 51 . The etch target layer 53 may be, for example, a silicon oxide layer, a silicon nitride layer, or a polysilicon layer. A first mask layer 55 is formed on the etch target layer 53 . The first mask layer 55 may be a material having an etch selectivity to that of the etch target layer 53 and may be, for example, an organic layer that does not include silicon. A second mask pattern 57 is formed on the first mask layer 55 . The second mask pattern 57 may be formed of a material having an etch selectivity to the first mask layer 55 . The width W1 of the second mask pattern 57 may correspond to the minimum line width that can be realized in the photolithography process. A distance W2 between the second mask patterns 57 may be greater than a width W1 of the second mask patterns 57 . For example, the width W1 to the spacing W2 may be about 3:5. Spacers 59 are formed to cover sidewalls of the second mask pattern 57 . A width W3 of the spacers 59 may correspond to about 1/3 of a width W1 of the second mask pattern 57 .

Referring to FIG. 12 , the second mask pattern 57 is removed. Then, the first mask layer 55 is etched using the spacers 59 as etch masks to form first mask patterns 55a. In this case, the interval between the first mask patterns 55a may be substantially equal to the width W1 of the second mask pattern 57 .

Referring to FIG. 13 , a third mask layer 61 is formed to conformally cover upper surfaces and sidewalls of the first mask patterns 55 . The third mask layer 61 may be, for example, a silicon oxide layer. A thickness T1 of the third mask layer 61 may be equal to a width W3 of the spacer 59 .

Referring to FIG. 14 , an organic layer 63 is formed on the third mask layer 61 . The organic layer 63 may be formed of an organic layer that does not include silicon. The organic layer 63 is formed to fill the spaces between the first mask patterns 55a.

Referring to FIG. 15 , a CMP process is performed on the organic layer 63 using the CMP composition. Accordingly, the organic layer 63 on the top surface of the third mask layer 61 is removed to expose the top surface of the third mask layer 61 , and organic layer patterns are formed between the first mask patterns 55a. (63a) is left.

Referring to FIG. 16 , an anisotropic etching process is performed on the exposed third mask layer 61 to remove the third mask layer 61 between the organic layer patterns 63a and the first mask pattern The fields 55a are exposed. In this case, third mask patterns 61a remain under the organic layer patterns 63a. In this case, a gap between the first mask pattern 55a and the organic layer pattern 63a may be formed to be the same as the width W3 of the spacer 59 .

Referring to FIG. 17 , the target layer 53 is etched using the first mask pattern 55a and the organic layer pattern 63a as an etch mask to form target layer patterns 53a. Then, the first and third mask patterns 55a and 61a and the organic layer pattern 63a are removed. Accordingly, it is possible to form a pattern having a line width smaller than the minimum line width achievable by the photolithography process.

The method described with reference to FIGS. 11 to 17 may be applied to a process of forming word lines or bit lines of a DRAM device.

18 is a schematic block diagram illustrating an example of a memory system including a semiconductor device manufactured according to embodiments of the present invention.

18, the memory system 1100 is a PDA, a portable computer, a web tablet (web tablet), a wireless phone (wireless phone), a mobile phone (mobile phone), a digital music player (digital music player), It can be applied to a memory card, or any device capable of transmitting and/or receiving information in a wireless environment.

The memory system 1100 includes a controller 1110 , a keypad, an input/output device 1120 such as a keyboard and a display, a memory 1130 , an interface 1140 , and a bus 1150 . Memory 1130 and interface 1140 communicate with each other via bus 1150 .

The controller 1110 includes at least one microprocessor, a digital signal processor, a microcontroller, or other processing devices similar thereto. Memory 1130 may be used to store instructions executed by the controller. The input/output device 1120 may receive data or signals from outside the system 1100 or may output data or signals to the outside of the system 1100 . For example, the input/output device 1120 may include a keyboard, a keypad, or a display device.

The memory 1130 includes non-volatile memory devices according to embodiments of the present invention. The memory 1130 may further include other types of memories, volatile memories that can be accessed at any time, and other various types of memories.

The interface 1140 serves to transmit data to or receive data from a communication network.

19 is a schematic block diagram illustrating an example of a memory card including a semiconductor device manufactured according to embodiments of the present invention.

Referring to FIG. 19 , a flash memory device 1210 according to the present invention is mounted on a memory card 1200 for supporting a high-capacity data storage capability. The memory card 1200 according to the present invention includes a memory controller 1220 that controls general data exchange between the host and the flash memory device 1210 .

The SRAM 1221 is used as the working memory of the processing unit 1222 . The host interface 1223 has a data exchange protocol of a host connected to the memory card 1200 . The error correction block 1224 detects and corrects errors included in data read from the multi-bit flash memory device 1210 . The memory interface 1225 interfaces with the flash memory device 1210 of the present invention. The processing unit 1222 performs various control operations for data exchange of the memory controller 1220 . Although not shown in the drawings, it is common knowledge in the art that the memory card 1200 according to the present invention may further include a ROM (not shown) for storing code data for interfacing with a host. It is self-evident to those who have acquired

According to the flash memory device and the memory card or the memory system of the present invention, a highly reliable memory system can be provided through the flash memory device 1210 having improved erase characteristics of dummy cells. In particular, the flash memory device of the present invention may be provided in a memory system such as a solid state disk (SSD) device, which has been actively conducted recently. In this case, a highly reliable memory system may be implemented by blocking a read error caused by the dummy cell.

20 is a schematic block diagram illustrating an example of an information processing system in which a semiconductor device manufactured according to embodiments of the present invention is mounted.

Referring to FIG. 20 , the flash memory system 1310 of the present invention is mounted in an information processing system such as a mobile device or a desktop computer. The information processing system 1300 according to the present invention includes a flash memory system 1310 and a modem 1320, a central processing unit 1330, a RAM 1340, and a user interface 1350 electrically connected to a system bus 1360, respectively. includes The flash memory system 1310 may be configured substantially the same as the aforementioned memory system or flash memory system. Data processed by the central processing unit 1330 or data input from the outside are stored in the flash memory system 1310 . Here, the above-described flash memory system 1310 may be configured as a semiconductor disk device (SSD). In this case, the information processing system 1300 may stably store a large amount of data in the flash memory system 1310 . In addition, as reliability increases, the flash memory system 1310 may reduce resources required for error correction, thereby providing a high-speed data exchange function to the information processing system 1300 . Although not shown, the information processing system 1300 according to the present invention may further include an application chipset, a camera image processor (CIS), an input/output device, and the like. It is self-evident to those who have acquired it.

In addition, the flash memory device or memory system according to the present invention may be mounted in various types of packages. For example, the flash memory device or memory system according to the present invention may include a package on package (PoP), ball grid arrays (BGAs), chip scale packages (CSPs), a plastic leaded chip carrier (PLCC), and a plastic dual in-line package. (PDIP), Die in Waffle Pack, Die in Wafer Form, Chip On Board(COB), Ceramic Dual In-Line Package(CERDIP), Plastic Metric Quad Flat Pack(MQFP), Thin Quad Flatpack(TQFP), Small Outline( SOIC), Shrink Small Outline Package(SSOP), Thin Small Outline(TSOP), Thin Quad Flatpack(TQFP), System In Package(SIP), Multi Chip Package(MCP), Wafer-level Fabricated Package(WFP), Wafer- It may be packaged and mounted in the same way as Level Processed Stack Package (WSP).

As mentioned above, although embodiments of the present invention have been described with reference to the accompanying drawings, those of ordinary skill in the art to which the present invention pertains can implement the present invention in other specific forms without changing its technical spirit or essential features. You can understand that there is Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

1, 51, 100: substrate
3, 23: gate interlayer insulating film
5, 25: sacrificial curtain
10, 20 110: structure
14, 14a, 63, 63a, 120, 120a, : organic film
12, 22: Hall
32: groove
115: recessed area
29, 34: buried insulating film
31: common drain region
34: gate insulating film
LSL: lower selection line
WL0, WL1, WL2, WL3: word line
USL0, USL1: upper selection line
BL: bit line
CSL: Common Source Line
53: etch target film
55, 55a, 57, 61, 61a: mask film
59: spacer

Claims (28)

delete delete delete delete delete delete delete delete delete delete forming a first structure including a first recessed region on the substrate;
filling the first recess region by forming an organic layer that does not include silicon on the first structure; and
performing a CMP process on the organic layer using a CMP slurry composition to remove at least a portion of the organic layer to expose the upper surface of the first structure;
The CMP slurry composition comprises:
0.001 to 5 wt% of oxide abrasive particles;
0.1-5% by weight of an oxidizing agent;
0-5 wt% of abrasive control agent;
0 to 3% by weight of surfactant;
0 to 3% by weight of a pH adjuster; and
79 to 99.889 wt% of deionized water,
An oxide film is disposed on the upper end of the first structure,
The method of manufacturing a semiconductor device in which the CMP slurry composition polishes the organic layer at a selectivity ratio of 6:1 or more with respect to the oxide layer. delete 12. The method of claim 11,
the first recess region is a first hole exposing the substrate;
After the CMP process is performed on the organic layer,
forming a second structure including a second hole exposing an upper surface of the organic layer on the first structure;
removing the organic layer through the second hole;
forming an active pillar covering at least sidewalls of the first hole and the second hole; and
The method of manufacturing a semiconductor device further comprising: forming a conductive line in a portion of the first structure and the second structure. 14. The method of claim 13,
Each of the first structure and the second structure has a structure in which a plurality of insulating films and sacrificial films are alternately stacked,
The step of forming a conductive line in a portion of the first structure and the second structure,
selectively removing the sacrificial layers; and
and forming the conductive line in a region from which the sacrificial layers are removed. 12. The method of claim 11,
The first structure may include an etch target layer disposed on the substrate, a plurality of first mask patterns disposed on the etch target layer in the form of parallel lines, and sidewalls and upper surfaces of the first mask patterns as cones. It includes a second mask film covering the foam,
The exposing of the upper surface of the first structure may include exposing the upper surface of the second mask layer. 16. The method of claim 15,
The interval between the first mask patterns is three times the thickness of the second mask layer,
A method of manufacturing a semiconductor device in which the organic layer is disposed between the first mask patterns. 16. The method of claim 15,
The method of claim 1 , further comprising: removing the exposed second mask layer by performing an anisotropic etching process and forming a second mask pattern under the organic layer. delete 12. The method of claim 11,
The removing of at least a portion of the organic layer is a method of manufacturing a semiconductor device in which the upper surface of the first structure is not exposed. 12. The method of claim 11,
The abrasive particles are _{at least one selected from silica (SiO 2} ), ceria (CeO ₂ ) and alumina (Al ₂ O ₃ ). Method of manufacturing a semiconductor device. 12. The method of claim 11,
The particle size of the abrasive particles is a method of manufacturing a semiconductor device of 30 ~ 120nm. 12. The method of claim 11,
The oxidizing agent is hydrogen peroxide, superoxide, dioxygenyl, ozone, ozonide, peroxide, fluorine, chlorine, chlorite (Chlorite), Chlorate, Perchlorate, Halogen Compounds, Nitric acid, Nitrate, Hypochlorite, Hypohalite, Chromium Trioxide ( Chromium trioxide, Pyridinium chlorochromate, Chromate, Dichromate, Chromium Compound, Potassium permanganate, Permanganate, Sodium perborate ( Sodium perborate), nitrous oxide (Nitrous Oxide), 2,2'-dipyridisulfide (2,2'-Dipyridisulfide), lead dioxide (PbO2), manganese dioxide (MnO2), copper oxide (CuO), iron chloride (FeCl3), A semiconductor device comprising at least one material selected from the group consisting of perchloric acid (HClO4), iron nitrate (Fe(NO)3), sulfate, and potassium thiosulfate (K2S2O8) manufacturing method. 12. The method of claim 11,
The polishing control agent is nitric acid, nitrate, sulfuric acid, peroxydisulfuric acid, peroxymonosulfuric acid, sulfonic acid, acetic acid, citric acid ( Citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, tartaric acid, chloric acid, chlorous acid, hypoa Hypochlorous acid, Perchloric acid, Halogen oxoacid, Ascorbic acid, Vinyl carboxylic acid, histidine, glycine, arginine, hydrochloric acid, hydrofluoric acid and phosphoric acid A method of manufacturing a semiconductor device which is at least one selected from the group comprising: 12. The method of claim 11,
The method of manufacturing a semiconductor device, wherein the surfactant is anionic or nonionic. 12. The method of claim 11,
The surfactant is a lauryl myristyl alcohol series, a methyl-oxirane polymer series having a hydrophile lipophile balance (HLB) value of 12 or more, ethylenediamine, ethoxylated and propoxyl At least one selected from ethoxylated and propoxylated alcohol series, 2-methyloxirane, oxirane series, polyethylene glycol, or polysorbate series A method of manufacturing a semiconductor device. 12. The method of claim 11,
The surfactant is benzalkonium chloride, alkyl benzene sulfonate (Alkyl Benzene Sulfonate), pemerol chloride (Phemerol chloride), ammonium lauryl sulfate (ammonium lauryl sulfate), sodium lauryl ether sulfate (sodium lauryl) ether sulfate, sodium myreth sulfate, dioctyl sodium sulfosuccinate, perfluorooctanesulfonate, perfluorobutanesulfonate, linear alkylbenzene sulfonate nate (linear alkylbenzene sulfonate), sodium stearate, sodium lauroyl sarcosinate, cetyl trimethylammonium bromide, cetyl trimethylammonium chloride, Perfluorononanoate, perfluorooctanoate, Octenidine dihydrochloride, 5-Bromo-5-nitro-1,3-dioxane -5-nitro-1,3-dioxane), dimethyldioctadecylammonium chloride, cetrimonium bromide, dioctadecyldimethylammonium bromide, octaethylene glycol mono dodecyl ether (Octaethylene glycol monododecyl ether), glyceryl laurate, or polyethoxyl A method of manufacturing a semiconductor device comprising at least one selected from polyethoxylated tallow amine. 12. The method of claim 11
The pH adjusting agent is at least one acid selected from the group consisting of polyacrylic acid, carboxylic acid, nitric acid, sulfuric acid and sulfonic acid, or potassium hydroxide, sodium hydroxide, aqueous ammonia, tetramethylammonium hydride A method of manufacturing a semiconductor device, wherein the base is at least one base selected from the group comprising: Tetramethylammonium hydroxide, Tetraethylammonium hydroxide, and Tetrabuthylammonium hydroxide. 12. The method of claim 11,
The composition is a method of manufacturing a semiconductor device having a pH of 2.0 to 5.0.

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